CN116515526B - Hydrogenation-active metal desulfurization combined process for catalytically cracked gasoline - Google Patents
Hydrogenation-active metal desulfurization combined process for catalytically cracked gasoline Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 112
- 239000002184 metal Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 36
- 230000023556 desulfurization Effects 0.000 title claims abstract description 36
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- 150000001336 alkenes Chemical class 0.000 claims abstract description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims description 72
- 229910052717 sulfur Inorganic materials 0.000 claims description 72
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 37
- 239000007791 liquid phase Substances 0.000 claims description 30
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 18
- 230000007704 transition Effects 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 23
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 229910052976 metal sulfide Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000013586 Complex regional pain syndrome type 1 Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a catalytic cracking gasoline hydrogenation-active metal desulfurization combined process, which comprises a hydrofining unit and an active metal desulfurization unit, wherein the active metal desulfurization unit comprises a reaction unit and a solid-liquid separation unit, and the active metal desulfurization unit can be arranged before or after the hydrofining unit, and is preferably arranged after the catalytic hydrofining unit. The combined process can optimize the operational range of hydrodesulfurization process conditions, avoid olefin transition saturation and effectively reduce the loss of the octane number of gasoline.
Description
Technical Field
The invention relates to a catalytic cracking gasoline hydrogenation-active metal desulfurization combined process, which can optimize the operational range of hydrodesulfurization process conditions and effectively control the olefin saturation degree.
Background
With the prominence of global pollution and the increasing awareness of environmental protection, china is greatly pushing the upgrade of finished oil quality in recent years, and the use of clean oil products is fully ensured under the guidance of policies and systems. Although new energy automobiles become an important research and development direction and popularization center of gravity in the automobile field, gasoline automobiles still play the most important role in traffic for a while, so that the requirement for clean gasoline is not reduced. The national VI gasoline standard, which was implemented since 2019, requires that the content of olefins and aromatics be continuously reduced while the sulfur content is controlled to be no more than 10 mug/g. And 70% of the commercial gasoline in China is processed by catalytic cracking gasoline.
In China, the sulfur content of the catalytic cracking gasoline is generally high and can reach 500-900ppm, some catalytic cracking gasoline can reach more than 1300 ppm, and meanwhile, the content of olefin is high and is generally between 35-40% (v). Therefore, the catalytic cracking gasoline must pass through a certain hydrodesulfurization and olefin saturation path to become applicable finished oil. However, in the catalytic cracking gasoline hydrofining process, there is a prominent contradiction point, namely, the process of removing impurity elements (sulfur, nitrogen and oxygen) by hydrogenation and the olefin hydrogenation saturation reaction are contradicted, and under severe conditions, such as increasing the hydrogenation reaction temperature, the impurity elements are beneficial to removing, so that a cleaner product is obtained, but at the same time, the olefin hydrogenation saturation reaction is also affected by the temperature, and the reaction depth is increased, so that the octane number loss of the product is serious, thereby seriously affecting the added value of the product.
To minimize octane number loss during the hydrofining process of the catalytic gasoline. Researchers often control high-selectivity desulfurization by means of developing a high-selectivity hydrodesulfurization catalyst, improving a process flow, optimizing process conditions and the like, and simultaneously, maintain a certain olefin hydrogenation saturation rate. Specific foreign successful applications include Prime-G+ technology from French Petroleum Institute (IFP), SCANfining technology from Exxon Mobil, and catalytic distillation technology from CD Tech. The domestic hydrodesulfurization refining technology mainly comprises RSDS technology of China petrochemical engineering institute (RIPP), DSO technology of China petrochemical engineering institute (Fushun) and OCT-M technology, FRS technology and OTA technology of China petrochemical engineering institute (FRIPP); however, in the existing technology, in order to achieve a deeper desulfurization rate, the process conditions are relatively harsh, and the control of the olefin saturation rate still has problems, so that the problems of complex processing process flow and relatively high investment cost also exist.
Disclosure of Invention
Aiming at the problems existing in the conventional hydrodesulfurization process, the invention provides a catalytic cracking gasoline hydrogenation-active metal desulfurization combined process, which combines an active metal desulfurization technology with a hydrodesulfurization technology, wherein olefin partial saturation and deep desulfurization reaction are carried out in two steps, the combined process can optimize the operational range of hydrodesulfurization process conditions, avoid olefin transition saturation and effectively reduce the octane number loss of gasoline.
A combined process of hydrogenation and active metal desulfurization of catalytic cracking gasoline, the combined process comprises a hydrofining unit and an active metal desulfurization unit, the active metal desulfurization unit comprises a reaction unit and a solid-liquid separation unit, and the active metal desulfurization unit can be arranged before or after the hydrofining unit, preferably after the catalytic hydrofining unit.
When the active metal desulfurization unit is arranged in front of the hydrofining unit, the catalytic cracking gasoline reacts with active metal firstly, and solid-liquid separation is carried out after the reaction; the liquid phase enters a hydrofining unit for reaction.
When the active metal desulfurization unit is arranged behind the hydrofining unit, the catalytic cracking gasoline is subjected to hydrofining reaction firstly, and the liquid phase product obtained after the hydrofining reaction is directly reacted with the active metal or separated.
In the combined process, the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content of the catalytic cracking gasoline is 200-850 ppm, preferably 320-650 ppm, and the volume content of olefin is 30-45, preferably 35-40. The combined process can treat the catalytic cracking gasoline with high sulfur content and high olefin content, and alleviate the operation condition of a catalytic cracking device.
In the combined process, the volume content of olefin in the hydrofined material is higher than 20%, preferably 20-30%, and more preferably 23-28%.
In the combined process, the reaction temperature of the hydrofining unit is 200-280 ℃, the reaction pressure is 1-3MPa, the volume space velocity is 1-4h -1, the hydrogen-oil volume ratio is 100-300, and moderate saturation of olefin is realized by adjusting the process conditions.
In the combined process, the hydrofining catalyst adopted by the hydrofining unit takes Al 2O3 as a carrier, moO 3 and CoO as active components, and the weight of the catalyst is taken as a reference, wherein the mass fraction of MoO 3 in the catalyst is 8-13%, and the mass fraction of CoO is 2-6%.
In the above combined process, the active metal comprises one or a mixture of several of Li, na and K, and the preferred active metal is Na.
In the combined process, the active metal desulfurization reaction can be performed in a CSTR reactor; before entering a CSTR reactor, the active metal can be heated to be in a liquid state and premixed with the catalytic cracking gasoline or with the hydrofined liquid phase product, and the full contact between the active metal and the liquid phase product can be promoted by means of ultrasonic dispersion, high-speed stirring, mixing shearing and the like in the premixing process. The volumetric space velocity of the active metal desulfurization unit corresponds to the ratio of the volumetric flow rate of the gasoline feed to the CSTR reactor volume.
In the combined process, when the catalytic cracking gasoline or the catalytic cracking gasoline subjected to hydrofining reacts with active metals, the reaction temperature is 150-320 ℃, the reaction pressure is 2-6MPa, the volume space velocity is 0.5-6 h -1, the hydrogen oil volume ratio is 100-300, and the molar ratio of the active metals to the sulfur (calculated by sulfur elements) content in the catalytic cracking gasoline raw material is 1-6, preferably 2-4.
In the above combined process, when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with the active metal, the introduced hydrogen contains hydrogen sulfide (based on the total volume of the hydrogen and the hydrogen sulfide) with a volume content of 5-20%, preferably 8-15%. The research result shows that the small amount of hydrogen sulfide contained in the hydrogen can promote the dispersion of alkali metal and shorten the residence time of the reaction.
In the combined process, the metal sulfide and unreacted active metal in the liquid phase material after the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with the active metal are converted into the active metal hydrosulfide through hydrogen sulfide or gas containing hydrogen sulfide. The catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metals, so that less alkali metal is needed, and alkali metal or alkali metal sulfide in the reacted materials is difficult to remove. In the method, hydrogen sulfide is introduced into the liquid phase material after the alkali metal reaction, so that metal sulfide and unreacted active metal are converted into active metal hydrosulfide, and then liquid-liquid separation is carried out, thereby improving the product separation efficiency. Research results show that the liquid active metal hydrosulfide is generated, is easier to gather and can be layered with diesel oil, and is easier to separate compared with the conventional process of generating solid sodium sulfide by desulfurizing metallic sodium, so that post-treatment processes such as water washing and the like are reduced.
The combined process of hydrogenation and active metal desulfurization of catalytically cracked gasoline can effectively reduce the operation conditions such as the temperature, the pressure and the like of hydrofining reaction, avoid the high-severity reaction conditions maintained by pursuing high desulfurization rate, and can deeply desulfurize materials under mild reaction conditions by the active metal desulfurization reaction, and simultaneously maintain certain olefin content and octane number. The method can process the full fraction catalytic cracking gasoline, omits a part of fractionating tower and device units such as mercaptan removal, simplifies the process flow and reduces the investment cost.
Detailed Description
The following examples and comparative examples are provided to further illustrate the production of high octane gasoline by a combination of catalytic cracking gasoline hydrogenation and active metal desulfurization processes, but are not intended to limit the process of the present invention.
The hydrofining catalyst adopted in the embodiment of the invention takes Al 2O3 as a carrier, co-Mo as an active component, and the weight of the catalyst is taken as a reference, wherein the mass fraction of MoO 3 in the catalyst is 10% and the mass fraction of CoO is 4%. The active metal is Na. The active metal desulfurization reaction is carried out in a Continuous Stirred Tank (CSTR) reactor; before entering a CSTR reactor, the active metal is heated to be in a liquid state and premixed with the catalytic cracking gasoline or with the hydrofined liquid phase product, and the premixing process is carried out under stirring.
Example 1
The active metal desulfurization unit is arranged before the hydrofining unit, the catalytic cracking gasoline reacts with active metal firstly, and liquid-liquid separation is carried out after the reaction; the liquid phase enters a hydrofining unit for reaction. The catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 220 ppm, and the volume content of olefin is 33%; when the catalytic cracking gasoline reacts with active metal Na, the reaction temperature is 180 ℃, the reaction pressure is 2 MPa, the volume space velocity is 6 h -1, the hydrogen-oil volume ratio is 100, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 2; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, then carrying out liquid-liquid separation, and feeding the material after the active metal hydrosulfide is removed into a hydrofining unit, wherein the average reaction temperature of the hydrofining unit is 200 ℃, the reaction pressure is 1 MPa, the volume space velocity is 2.5 h -1, and the hydrogen-oil volume ratio is 200. In the finally obtained gasoline product, the volume content of olefin is 24%, the sulfur content is 4ppm, the octane number of the gasoline is 90.6, and no Na residue exists in the gasoline.
Example 2
The active metal desulfurization unit is arranged before the hydrofining unit, the catalytic cracking gasoline reacts with active metal firstly, and solid-liquid separation is carried out after the reaction; the liquid phase enters a hydrofining unit for reaction. The catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 530 ppm, and the olefin volume content is 38%; when the catalytic cracking gasoline reacts with active metal Na, the reaction temperature is 240 ℃, the reaction pressure is 4MPa, the volume space velocity is 3h -1, the hydrogen oil volume ratio is 200, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 4; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, then carrying out liquid-liquid separation, and feeding the material after the active metal hydrosulfide is removed into a hydrofining unit, wherein the average reaction temperature of the hydrofining unit is 240 ℃, the reaction pressure is 2 MPa, the volume space velocity is 1.8h -1, and the hydrogen-oil volume ratio is 200. In the finally obtained gasoline product, the volume content of olefin is 27%, the sulfur content is 7 ppm, the octane number of the gasoline is 91.0, and no Na residue exists in the gasoline.
Example 3
The active metal desulfurization unit is arranged before the hydrofining unit, the catalytic cracking gasoline reacts with active metal firstly, and solid-liquid separation is carried out after the reaction; the liquid phase enters a hydrofining unit for reaction. The catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 784 ppm, and the volume content of olefin is 42%; when the catalytic cracking gasoline reacts with active metal Na, the reaction temperature is 280 ℃, the reaction pressure is 6MPa, the volume space velocity is 0.75 h -1, the hydrogen-oil volume ratio is 300, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 6; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, then carrying out liquid-liquid separation, and feeding the material after the active metal hydrosulfide is removed into a hydrofining unit, wherein the average reaction temperature of the hydrofining unit is 280 ℃, the reaction pressure is 3 MPa, the volume space velocity is 1h -1, and the hydrogen oil volume ratio is 300. In the finally obtained gasoline product, the volume content of olefin is 29%, the sulfur content is 9 ppm, the octane number of the gasoline is 92.2, and no Na is remained in the gasoline.
Example 4
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 245 ppm, and the volume content of olefin is 33%; the average reaction temperature of the hydrofining unit is 210 ℃, the reaction pressure is 1MPa, the volume space velocity is 3h -1, and the hydrogen-oil volume ratio is 100; when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metal Na, the reaction temperature is 200 ℃, the reaction pressure is 2 MPa, the volume space velocity is 4 h -1, the volume ratio of hydrogen oil is 100, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 2; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 24%, the sulfur content is 5ppm, the octane number of the gasoline is 90.5, and no Na residue exists in the gasoline.
Example 5
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 476 ppm, and the volume content of olefin is 37%; the average reaction temperature of the hydrofining unit is 250 ℃, the reaction pressure is 2MPa, the volume space velocity is 2h -1, and the hydrogen-oil volume ratio is 200; when the catalytic cracking gasoline or the catalytic cracking gasoline subjected to hydrofining reacts with active metal Na, the reaction temperature is 230 ℃, the reaction pressure is 4 MPa, the volume space velocity is 2h -1, the volume ratio of hydrogen oil is 200, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 3; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 25%, the sulfur content is 6 ppm, the octane number of the gasoline is 91.1, and no Na is remained in the gasoline.
Example 6
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 784 ppm, and the volume content of olefin is 42%; the average reaction temperature of the hydrofining unit is 270 ℃, the reaction pressure is 3 MPa, the volume space velocity is 1.5 h -1, and the hydrogen-oil volume ratio is 300; when the catalytic cracking gasoline or the catalytic cracking gasoline subjected to hydrofining reacts with active metal Na, the reaction temperature is 300 ℃, the reaction pressure is 6 MPa, the volume space velocity is 0.67 h -1, the volume ratio of hydrogen to oil is 300, and the molar ratio of the active metal to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 5; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 29%, the sulfur content is 4 ppm, the octane number of the gasoline is 92.7, and no Na is remained in the gasoline.
Example 7
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 245 ppm, and the volume content of olefin is 33%; the average reaction temperature of the hydrofining unit is 210 ℃, the reaction pressure is 1MPa, the volume space velocity is 3h -1, the hydrogen-oil volume ratio is 100, and the hydrogen sulfide volume content in the introduced hydrogen is 5%; when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metal Na, the reaction temperature is 200 ℃, the reaction pressure is 2 MPa, the volume space velocity is 6 h -1, the volume ratio of hydrogen oil is 100, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 2; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 24%, the sulfur content is 3 ppm, the octane number of the gasoline is 90.5, and no Na is remained in the gasoline.
Example 8
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 476 ppm, and the volume content of olefin is 37%; the average reaction temperature of the hydrofining unit is 250 ℃, the reaction pressure is 2 MPa, the volume space velocity is 2h -1, the hydrogen-oil volume ratio is 200, and the hydrogen sulfide volume content in the introduced hydrogen is 10%; when the catalytic cracking gasoline or the catalytic cracking gasoline subjected to hydrofining reacts with active metal Na, the reaction temperature is 230 ℃, the reaction pressure is 4MPa, the volume space velocity is 3h -1, the volume ratio of hydrogen oil is 200, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 3; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 26%, the sulfur content is 4 ppm, the octane number of the gasoline is 91.1, and no Na is remained in the gasoline.
Example 9
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 784 ppm, and the volume content of olefin is 42%; the average reaction temperature of the hydrofining unit is 270 ℃, the reaction pressure is 3MPa, the volume space velocity is 1.5 h -1, the hydrogen-oil volume ratio is 300, and the hydrogen sulfide volume content in the introduced hydrogen is 15%; when the catalytic cracking gasoline or the catalytic cracking gasoline subjected to hydrofining reacts with active metal Na, the reaction temperature is 300 ℃, the reaction pressure is 6MPa, the volume space velocity is 1.5 h -1, the volume ratio of hydrogen oil is 300, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 5; introducing hydrogen sulfide gas into the liquid phase material obtained after the reaction to convert metal sulfide and unreacted active metal in the material into active metal hydrosulfide, and then carrying out liquid-liquid separation; in the finally obtained gasoline product, the volume content of olefin is 29%, the sulfur content is 2 ppm, the octane number of the gasoline is 92.8, and no Na is remained in the gasoline.
Example 10
The catalytic cracking gasoline is subjected to hydrofining reaction firstly, and a liquid phase product obtained after separating materials subjected to hydrofining reaction reacts with active metal; the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 245 ppm, and the volume content of olefin is 33%; the average reaction temperature of the hydrofining unit is 230 ℃, the reaction pressure is 1.5 MPa, the volume space velocity is 2.5h -1, the hydrogen-oil volume ratio is 150, and the hydrogen sulfide volume content in the introduced hydrogen is 5%; when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metal Na, the reaction temperature is 200 ℃, the reaction pressure is 2 MPa, the volume space velocity is 6 h -1, the volume ratio of hydrogen oil is 200, and the molar ratio of the active metal consumption to the sulfur (calculated by sulfur element) content in the catalytic cracking gasoline raw material is 3. And (5) carrying out solid-liquid separation by using a centrifugal method. In the finally obtained gasoline product, the volume content of olefin is 24%, the sulfur content is 3 ppm, the octane number of the gasoline is 90.3, and the Na content in the gasoline is 33.2 ppm.
Comparative example 1
When the catalytic cracking gasoline only carries out hydrofining reaction, the catalytic cracking gasoline is taken from high-sulfur gasoline of a catalytic cracking device of a refinery, the sulfur content in the catalytic cracking gasoline is 476 ppm, and the volume content of olefin is 37%; the average reaction temperature of the hydrofining unit is 220 ℃, the reaction pressure is 1MPa, the volume space velocity is 1.5 h -1, and the hydrogen-oil volume ratio is 200. In the finally obtained gasoline product, the volume content of olefin is 29%, the sulfur content is 87 ppm, and the octane number of the gasoline is 90.4.
Comparative example 2
When the catalytic cracking gasoline only carries out hydrofining reaction, the catalytic cracking gasoline is taken from high-sulfur gasoline of a catalytic cracking device of a refinery, the sulfur content in the catalytic cracking gasoline is 476 ppm, and the volume content of olefin is 37%; the average reaction temperature of the hydrofining unit is 280 ℃, the reaction pressure is 2MPa, the volume space velocity is 1.5 h -1, and the hydrogen-oil volume ratio is 300. In the finally obtained gasoline product, the volume content of olefin is 11%, the sulfur content is 9 ppm, and the octane number of the gasoline is 88.5.
Claims (16)
1. A catalytic cracking gasoline hydrogenation-active metal desulfurization combined process is characterized in that: the combined process comprises a hydrofining unit and an active metal desulfurization unit, wherein the active metal desulfurization unit comprises a reaction unit and a solid-liquid separation unit, and the active metal desulfurization unit is arranged before or after the hydrofining unit and is used for heating active metal to be in a liquid state and premixing with catalytically cracked gasoline or liquid phase products after hydrofining; the hydrofining catalyst adopted by the hydrofining unit takes Al 2O3 as a carrier, takes MoO 3 and CoO as active components, and takes the weight of the catalyst as a reference, wherein the mass fraction of MoO 3 in the catalyst is 8-13% and the mass fraction of CoO is 2-6%; the active metal comprises one or a mixture of several of Li, na and K.
2. The process according to claim 1, characterized in that: the active metal desulfurization unit is arranged after the catalytic hydrofining unit.
3. The process according to claim 1, characterized in that: when the active metal desulfurization unit is arranged in front of the hydrofining unit, the catalytic cracking gasoline reacts with active metal firstly, and solid-liquid separation is carried out after the reaction; the liquid phase enters a hydrofining unit for reaction.
4. The process according to claim 1, characterized in that: when the active metal desulfurization unit is arranged behind the hydrofining unit, the catalytic cracking gasoline is subjected to hydrofining reaction firstly, and the liquid phase product obtained after the hydrofining reaction is directly reacted with the active metal or separated.
5. The process according to claim 1, characterized in that: the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 200-850 ppm, and the volume content of olefin is 30-45%.
6. The process according to claim 5, wherein: the catalytic cracking gasoline is high-sulfur gasoline obtained from a catalytic cracking device of a refinery, wherein the sulfur content in the catalytic cracking gasoline is 320-650 ppm, and the volume content of olefin is 35-40%.
7. The process according to claim 1, characterized in that: the volume content of olefin in the hydrofined material is higher than 20%.
8. The process according to claim 7, wherein: the volume content of olefin in the hydrofined material is 20-30%.
9. The process according to claim 7, wherein: the volume content of olefin in the hydrofined material is 23-28%.
10. The process according to claim 1, characterized in that: the reaction temperature of the hydrofining unit is 200-280 ℃, the reaction pressure is 1-3MPa, the volume space velocity is 1-4h -1, and the hydrogen-oil volume ratio is 100-300.
11. The process according to claim 1, characterized in that: the active metal is Na.
12. The process according to claim 1, characterized in that: the active metal desulfurization reaction is carried out in a CSTR reactor; before entering the CSTR reactor, the active metal is heated to a liquid state and premixed with the catalytically cracked gasoline or with the hydrofined liquid phase product.
13. The process according to claim 1, characterized in that: when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metals, the reaction temperature is 150-320 ℃, the reaction pressure is 2-6MPa, the volume space velocity is 0.5-6 h -1, the volume ratio of hydrogen to oil is 100-300, and the content mole ratio of the active metals to sulfur contained in the catalytic cracking gasoline raw material calculated by sulfur element is 1-6.
14. The process according to claim 13, wherein: the molar ratio of the active metal amount to the sulfur content in the catalytically cracked gasoline material, calculated as sulfur element, is 2-4.
15. The process according to claim 1, characterized in that: when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metals, the introduced hydrogen contains hydrogen sulfide with the volume content of 5-20 percent.
16. The process according to claim 15, wherein: when the catalytic cracking gasoline or the catalytic cracking gasoline after hydrofining reacts with active metals, the introduced hydrogen contains 8-15% hydrogen sulfide by volume.
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| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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| CN1323755C (en) * | 2004-10-18 | 2007-07-04 | 中国石油化工集团公司 | Method for preparing hydrogenation aromatization catalyst |
| CN101724442B (en) * | 2008-10-28 | 2012-11-21 | 中国石油化工股份有限公司 | Method for reducing octane number loss of gasoline deep hydrodesulphurization |
| JP4929311B2 (en) * | 2009-04-27 | 2012-05-09 | 一般財団法人石油エネルギー技術センター | Hydrodesulfurization catalyst and hydrodesulfurization method for gasoline fraction |
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| CN103074106B (en) * | 2011-10-25 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of method reducing content of sulfur in gasoline |
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