CN116622406A - Process for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline - Google Patents
Process for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline Download PDFInfo
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- CN116622406A CN116622406A CN202210838105.9A CN202210838105A CN116622406A CN 116622406 A CN116622406 A CN 116622406A CN 202210838105 A CN202210838105 A CN 202210838105A CN 116622406 A CN116622406 A CN 116622406A
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- gasoline
- catalytic cracking
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- aromatic hydrocarbon
- aromatization
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- 239000003502 gasoline Substances 0.000 title claims abstract description 135
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 59
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 51
- 230000008569 process Effects 0.000 title claims abstract description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 47
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 73
- 239000007789 gas Substances 0.000 claims description 45
- 239000002808 molecular sieve Substances 0.000 claims description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 31
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007233 catalytic pyrolysis Methods 0.000 abstract 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 7
- 238000004230 steam cracking Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- -1 alcohol amine Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/20—C2-C4 olefins
-
- 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
- C10G2400/30—Aromatics
-
- 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
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)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a process method for producing olefin and aromatic hydrocarbon by catalytically cracking gasoline, belonging to the technical field of petrochemical product processing. The process method comprises the following steps: sending the catalytic cracking gasoline into an atmospheric distillation device for separation to obtain a light gasoline fraction and a heavy gasoline fraction; then, the light gasoline fraction is sent to a catalytic cracking device for treatment to obtain C 1 ‑C 4 Component and C 5 + A component separating said heavy gasoline fraction and said C 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon. The process method provided by the invention is different from the prior art that the hydrodesulfurization and olefin reduction of the catalytic pyrolysis gasoline are carried out, namely, the catalytic pyrolysis gasoline is directly distilled under normal pressure and then is respectively subjected to catalytic pyrolysis and aromatization treatment, so that the low-grade gasoline can be producedThe process flow is novel, the low-carbon olefin and the light aromatic hydrocarbon can be produced to the maximum extent, the requirements of the market on chemicals can be met, and the economic benefit can be improved.
Description
Technical Field
The invention belongs to the technical field of petrochemical product processing, and particularly relates to a process method for producing olefin and aromatic hydrocarbon by catalytically cracking gasoline.
Background
At present, catalytic cracking devices of refining enterprises are still the most important production devices for producing the motor gasoline, and the catalytic cracking gasoline is a main component of the motor gasoline in China, and accounts for about 70% of the whole gasoline. However, with the acceleration of the economic high-quality development process of China, the addition of factors such as poor oil refining profit capability, continuously improved electric automobile occupancy and the like, the consumption of gasoline in China in 2020 is 116Mt, the acceleration in the next 5 years is expected to be gradually slowed down, and the peak value of about 156Mt in 2025 years is expected to be reached, so that the surplus of the gasoline productivity, in particular the surplus of the catalytic cracking gasoline productivity, is inevitably caused. On the other hand, the olefin and the aromatic hydrocarbon are used as the most basic raw materials of the organic synthetic materials, and the market supply is always in a shortage state, so that the catalytic cracking gasoline is converted into the olefin and the aromatic hydrocarbon, which not only can meet the urgent market demand, but also has better economic benefit.
The processing of catalytically cracked gasoline in China mainly produces clean gasoline by desulfurizing and reducing olefin (such as hydrodesulfurization), and few chemicals such as olefin, aromatic hydrocarbon and the like are considered in the production of catalytically cracked gasoline. Patent document CN108456552B discloses a method for producing chemical products using catalytically cracked gasoline, which cuts the pre-hydrocracked gasoline into a light fraction, a middle fraction and a heavy fraction; extracting the middle distillate by using a solvent to obtain raffinate oil rich in olefin and extract oil rich in aromatic hydrocarbon; carrying out mild aromatization on the raffinate oil to obtain an aromatization product; recovering light olefins from the extracted oil to obtain light olefins and sulfur-rich oil; carrying out selective hydrodesulfurization on the heavy fraction and sulfur-rich oil to obtain a desulfurization heavy fraction; carrying out aromatic extraction or extractive distillation on the aromatization product and the desulfurization heavy fraction; the technical proposal is that the catalytic cracking gasoline is used as raw material to produce products such as extract oil, light olefin, aromatization, etc., but the catalytic cracking gasoline is still subjected to hydrogenation treatment.
Therefore, how to convert catalytically cracked gasoline into olefins and aromatics becomes a problem to be solved in order to meet market demands and improve economic benefits of refinery enterprises.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a process method for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline, which is characterized in that the catalytic cracking gasoline is directly distilled under normal pressure and then is respectively subjected to catalytic cracking and aromatization treatment, so that low-carbon olefin and light aromatic hydrocarbon can be produced, the treatment process flow is novel, the process flow is short, the investment is saved, and the operation cost is low.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for producing olefins and aromatics from catalytically cracked gasoline, comprising: sending the catalytic cracking gasoline into an atmospheric distillation device for separation to obtain a light gasoline fraction and a heavy gasoline fraction; then, the light gasoline fraction is sent to a catalytic cracking device for treatment to obtain C 1 -C 4 Component and C 5 + A component separating said heavy gasoline fraction and said C 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon.
As a still further preferable aspect of the invention, the C 1 -C 4 The components are separated to obtain first dry gas, propylene, propane and C 4 The components are as follows.
As a still further preferred aspect of the present invention, C 1 -C 4 C obtained by separating components 4 One part of the components is returned to the catalytic cracking device for recycling, and the other part is mixed with propane to directly serve as liquefied petroleum gas products.
As a further preferred mode of the technical scheme of the invention, the temperature for separating the light gasoline from the heavy gasoline in the atmospheric distillation device is 65-95 ℃.
Still more preferably, according to the present invention, the reactor of the catalytic cracking apparatus is one selected from a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.
As a further preferable mode of the technical scheme of the invention, the reaction temperature of the catalytic cracking device is 450-750 ℃, the system pressure is 0-1MPa, and the feeding airspeed is 0.5-5h -1 。
As a still further preferred embodiment of the present invention, the catalyst in the catalytic cracking device is constituted by: the active component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And Ce (Ce) 2 O 3 。
As a further preferred aspect of the present invention, the mass content of each component of the catalyst in the catalytic cracking device is: 40-80% HZSM-5 molecular sieve, 20-60% catalyst carrier, 1-5% P 2 O 5 、1-5％Ce 2 O 3 。
As a further preferred aspect of the present invention, the HZSM-5 molecular sieve in the catalytic cracking catalyst has a silica-alumina ratio of 60 to 150.
As a still further preferred embodiment of the present invention, the reactor of the aromatization apparatus is one selected from the group consisting of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.
As a further preferred mode of the technical scheme of the invention, the reaction temperature of the aromatization device is 450-550 ℃, the system pressure is 0-2MPa, and the feed is fedSpace velocity of 0.3-3h -1 。
As a still further preferred embodiment of the present invention, the catalyst in the aromatization apparatus is constituted by: the active component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And ZnO.
As a further preferred aspect of the present invention, the mass content of each component of the catalyst in the aromatization apparatus is: 50-90% HZSM-5 molecular sieve, 10-50% catalyst carrier, 1-5% P 2 O 5 、1-5％ZnO。
As a further preferred aspect of the present invention, the HZSM-5 molecular sieve in the aromatization catalyst has a silica/alumina ratio of from 30 to 90.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a process method for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline, which is different from the prior art that the catalytic cracking gasoline is subjected to hydrodesulfurization and olefin reduction.
(2) The process method for producing olefin and aromatic hydrocarbon by using the catalytic cracking gasoline provided by the invention has no special requirements on the catalytic cracking gasoline raw material, and the process method can be used for preparing stable gasoline of a catalytic cracking device or crude gasoline produced by the catalytic cracking device, and has strong raw material adaptability.
(3) The invention provides a method for directly producing olefin and aromatic hydrocarbon by catalytically cracking gasoline, which is C produced by a catalytic cracking device 4 The recycling of the components can produce more ethylene and propylene.
(4) The invention utilizes advanced olefin catalytic cracking technology and catalyst technology, not only the raw material olefin is cracked into ethylene and propylene, but also the sulfur-containing compound in the light gasoline is converted into H 2 S, thereby removing H by using a conventional alcohol amine method 2 S achieves the purpose of gas desulfurization, and ensures that the sulfide content in ethylene and propylene is not higher than the actual use requirement.
(5) In the invention, C produced by catalytic cracking 5 + The components and the heavy gasoline fraction are subjected to aromatization together, so that the two raw materials can be fully utilized to form the light aromatic hydrocarbon in the maximum quantity.
(6) The invention utilizes advanced aromatization catalyst technology, and besides the maximum production of aromatic hydrocarbon, the aromatization catalyst can also convert sulfur-containing compounds in the raw materials into H 2 S, and H can be removed by using a conventional alcohol amine method 2 S, so that the sulfur content of the mixed aromatic hydrocarbon is very low, and the practical use requirement of the aromatic hydrocarbon is ensured.
(7) The liquefied petroleum gas produced by the invention is a high-quality raw material for preparing ethylene by steam cracking.
In a word, the process method for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline provided by the invention optimizes the catalytic cracking gasoline according to the composition of the catalytic cracking gasoline family, can furthest produce low-carbon olefin and light aromatic hydrocarbon, can meet the demands of the market on chemicals, and can improve the economic benefit.
Drawings
FIG. 1 is a schematic flow chart of a process for producing light olefins and light aromatics from catalytically cracked gasoline according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Meanwhile, it should be emphasized that the specific conditions are not noted in the examples, and are performed according to conventional conditions or conditions suggested by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Referring to fig. 1, in this embodiment, a process for producing olefins and aromatics from catalytically cracked gasoline comprises the following steps: the catalytic cracking gasoline is sent into an atmospheric distillation device for separation,obtaining a light gasoline fraction and a heavy gasoline fraction; then, the light gasoline fraction is sent to a catalytic cracking device for treatment to obtain C 1 -C 4 Component and C 5 + A component separating said heavy gasoline fraction and said C 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon.
In the embodiment, the raw material of the catalytic cracking gasoline can be the crude gasoline produced by a catalytic cracking device or the stable gasoline produced by the catalytic cracking device, and the raw material has wide adaptability.
In the embodiment, a process route of catalytic cracking and aromatization treatment is adopted after atmospheric distillation, and the principle is as follows: the olefins in the gasoline are mainly distributed in C 5 -C 7 In C 5 -C 6 The majority; aromatic hydrocarbon in gasoline is distributed in C 7 -C 11 In C 8 -C 9 Most (see table 1). According to the catalytic cracking reaction principle of petroleum hydrocarbon, the catalytic cracking of olefin is easier to generate low-carbon olefin such as ethylene, propylene and the like, so that the catalytic cracking light gasoline can produce the ethylene and the propylene in the largest quantity through the catalytic cracking, and meanwhile, the byproduct C rich in aromatic hydrocarbon is produced 5 + A fraction; in addition, the catalytic cracking heavy gasoline is rich in aromatic hydrocarbon, non-aromatic hydrocarbon is converted into light aromatic hydrocarbon (benzene, toluene and xylene) through a light hydrocarbon aromatization technology, and meanwhile, the heavy aromatic hydrocarbon is converted into light aromatic hydrocarbon through a dealkylation technology, so that the aim of producing more light aromatic hydrocarbon is fulfilled.
TABLE 1 typical catalytic cracking gasoline family composition (PONA) distribution
| Carbon number | P (Paraffin) | N (cycloparaffin) | O (olefins) | A (aromatic hydrocarbon) | Totalizing |
| 4 | 1.42 | 6.38 | 7.8 | ||
| 5 | 7.30 | 0.14 | 14.28 | 21.72 | |
| 6 | 5.36 | 1.48 | 11.67 | 0.34 | 18.85 |
| 7 | 2.85 | 1.90 | 7.91 | 2.56 | 15.22 |
| 8 | 2.92 | 1.77 | 4.05 | 6.16 | 14.9 |
| 9 | 2.90 | 1.28 | 0.85 | 6.43 | 11.46 |
| 10 | 1.16 | 0.36 | 5.63 | 7.15 | |
| 11 | 0.78 | 1.42 | 2.2 | ||
| 12 | 0.21 | 0.21 | |||
| Totalizing | 24.90 | 6.93 | 45.14 | 22.54 | 99.51 |
In this example, the catalytically cracked gasoline was separated by a vacuum distillation apparatus to obtain a light gasoline fraction and a heavy gasoline fraction. It can be understood that the atmospheric distillation device can realize the functions of dividing the catalytic cracking gasoline into a light fraction and a heavy fraction, and the common atmospheric distillation tower can realize the above-mentioned processing functions, and the structure and the characteristics of the atmospheric distillation device are not specifically described in the embodiment.
In the embodiment, the temperature for separating the light gasoline from the heavy gasoline in the atmospheric distillation device is 65-95 ℃; preferably 75-85 ℃. It will be appreciated that in this embodiment the separation temperature may be any specific value of 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃ or any value in the range of 65-95 ℃, and the specific temperature may be flexibly adjusted to the fractionation temperature according to the actual situation (the olefin content in the feed components varies and the downstream olefin and aromatic hydrocarbon demands).
In this example, the light gasoline fraction is sent to a catalytic cracking device for treatment to obtain C 1 -C 4 Component and C 5 + A component (C); c obtained by catalytic cracking of heavy gasoline fraction and light gasoline fraction 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon. C obtained by sending light gasoline fraction into catalytic cracking device 1 -C 4 The components are in gaseous state, and are further processed by a general gas separation device to obtain a first dry gas (C) 1 -C 2 Component), propylene, propane, C 4 A component (C); wherein the ethylene in the first dry gas can be either directly utilized (e.g., by alkylation techniques to produce ethylbenzene) or separatedPure ethylene is produced for chemical utilization; the pure propylene obtained by separation can be used in chemical industry; the propane obtained by separation is used as a part of liquefied gas; wherein the C is isolated 4 A part of the components are returned to the catalytic cracking unit for further catalytic cracking to produce ethylene and propylene; another part C 4 The components can be combined with propane to be delivered as liquefied petroleum gas, and can also be used as raw materials for preparing ethylene by steam cracking (because the liquefied petroleum gas is mainly alkane). It will be appreciated that C 1 -C 4 The separation of the components involves the separation of the components of the low-carbon array, which is a mature prior art, and the process flow, the device structure and the characteristics of the components are not specifically described in the embodiment, so that the above processing functions can be realized.
In this example, the heavy and light gasoline fractions were catalytically cracked to obtain C 5 + The components enter a light hydrocarbon aromatization device together for aromatization reaction to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon, and the second dry gas, the liquefied gas and the mixed aromatic hydrocarbon are aromatized together, so that the light aromatic hydrocarbon can be produced in maximum amount by fully utilizing the raw materials of the second dry gas, the liquefied gas and the mixed aromatic hydrocarbon, and the maximization of the production economic value of chemical products is realized.
In this example, the (second) dry gas produced by the aromatization apparatus may be used as a plant fuel gas, or may be separated to produce hydrogen and as an ethane feedstock for producing ethylene by steam cracking.
In this embodiment, C 1 -C 4 C obtained by separating components 4 The components and the liquefied gas generated by the aromatization device are combined to be delivered as liquefied petroleum gas, and can also be used as raw materials for preparing ethylene by steam cracking.
In this embodiment, benzene, toluene and xylene are obtained by separating and converting the mixed aromatic hydrocarbon generated by the aromatization device. It is understood that the benzene tower, the toluene tower, the xylene tower and other preceding or subsequent processing units involved in the separation and conversion process are all mature prior art, and the structures and features of the benzene tower, the toluene tower, the xylene tower and other preceding or subsequent processing units are not specifically described in the embodiment, so that the above processing functions can be realized.
In this embodiment, the reactor used in the catalytic cracking apparatus may be one of a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor; preferably, the fluidized bed reactor is not particularly limited in its specific structure and form in this example.
In this embodiment, the main process parameters of the catalytic cracking device are as follows: the reaction temperature is 450-750 ℃, the system pressure is 0-1MPa, and the feeding airspeed is 0.5-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 550-650 ℃, the system pressure is 0.1-0.3MPa, and the feeding airspeed is 1-3h -1 . It will be appreciated that the reaction temperature in this embodiment may be any specific value of 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃ or any value in the range of 450-750 ℃; the system pressure can be any specific value of 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa and 0.3MPa or any value in the range of 0-1 MPa; the space velocity of the feed can be 1h -1 、1.5h -1 、2h -1 、2.5h -1 、3h -1 Any specific value of (a) is alternatively 0.5-5h -1 Any number within the range.
In this embodiment, the catalyst used in the catalytic cracking apparatus is constituted by: the active component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And Ce (Ce) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Further, the mass content of each component in the catalyst is as follows: 40-80% HZSM-5 molecular sieve, 20-60% catalyst carrier, 1-5% P 2 O 5 、1-5Ce 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the mass content of each component in the catalyst is as follows: 50-70% HZSM-5 molecular sieve, 30-50% catalyst carrier, 2-3% P 2 O 5 、1.5-2.5Ce 2 O 3 . It will be appreciated that the HZSM-5 molecular sieve may have a mass fraction of any particular value of 50%, 55%, 60%, 65%, 70% or any value in the range of 40-80% based on 100% total; catalyst support Al 2 O 3 The mass ratio of (2) may be any specific value of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or any value in the range of 20-60%; p (P) 2 O 5 Can be of the mass ratio ofAny specific value of 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% or any value in the range of 1-5%; ce (Ce) 2 O 3 The mass ratio of (c) may be any specific value of 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5% or any value in the range of 1 to 5%.
In the embodiment, the silicon-aluminum ratio of the HZSM-5 molecular sieve in the catalytic cracking catalyst is 60-150; more preferably, from 90 to 120; it will be appreciated that the HZSM-5 molecular sieve may have a silica to alumina ratio of any particular value of 90, 95, 100, 105, 110, 115, 120 or any value in the range of 60-150.
In this embodiment, a method for preparing the catalytic cracking catalyst is provided: taking 500-1000kg (Al) of aluminum sol 2 O 3 200-500kg of water and pseudo-boehmite are slowly added while stirring, 250-750kg of HZSM-5 molecular sieve with the silicon-aluminum ratio of 60-150 is slowly added while stirring after stirring for 0.5-5h, and then stirring is carried out for 0.5-12h; then spray drying and forming under the conditions of the hearth temperature of 350-450 ℃, the outlet temperature of 150-250 ℃ and the spray pressure of 3-5 MPa; then roasting for 0.5-12h at 500-700 ℃; and (3) carrying out equal volume saturated impregnation on the roasted catalyst by using an ammonium dihydrogen phosphate aqueous solution and a cerium nitrate aqueous solution, drying the impregnated catalyst at 100-200 ℃ for 0.5-12h, and roasting at 500-700 ℃ for 0.5-12h to obtain the finished catalyst for the catalytic cracking light gasoline fraction. Finished catalyst P 2 O 5 And Ce (Ce) 2 O 3 The content is 1-5% and 1-5% respectively. Obviously, the catalytic cracking catalyst is not limited to the specific limitation of the above process parameters, for example, the addition amount of the raw materials such as alumina sol, pseudo-boehmite, HZSM-5 molecular sieve, ammonium dihydrogen phosphate aqueous solution, cerium nitrate aqueous solution and the like can be adjusted; for example, the hearth temperature can be 380 ℃, 390 ℃, 410 ℃, 420 ℃ and the like; the outlet temperature of spray drying can be 190 ℃, 210 ℃ and the like, and the spray pressure can be 3.8MPa, 3.9MPa, 4.1MPa, 4.2MPa and the like; the baking temperature after spray drying can be 580 deg.C, 590 deg.C, 610 deg.C, 620 deg.C, etc., and the baking is performedThe interval can be 3.5h, 4h, 4.5h, 5.5h, 6h, 6.5h and the like; the drying temperature of the impregnated catalyst may be 135 ℃, 145 ℃, 155 ℃, 165 ℃, etc., and the drying time may be 3.5 hours, 4 hours, 4.5 hours, 5.5 hours, 6 hours, 6.5 hours, etc.; the final roasting temperature can be 580 ℃, 590 ℃, 610 ℃, 620 ℃ and the like, and the roasting time can be 3.5h, 4h, 4.5h, 5.5h, 6h, 6.5h and the like.
As a more specific description, the present embodiment provides a specific preparation method of the catalytic cracking catalyst: 710kg of aluminum sol (Al) 2 O 3 The content of the sodium silicate is 21 percent), 530kg of water and pseudo-boehmite are slowly added while stirring, 500kg of HZSM-5 molecular sieve with the silicon-aluminum ratio of 120 is slowly added while stirring after stirring for 2 hours, and then stirring is carried out for 5 hours; then, spray drying and forming are carried out under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4MPa, and then roasting is carried out for 5 hours at 600 ℃; and (3) carrying out equal volume saturated impregnation on the roasted catalyst by using an ammonium dihydrogen phosphate aqueous solution and a cerium nitrate aqueous solution, drying the impregnated catalyst at 150 ℃ for 5 hours, and roasting at 600 ℃ for 5 hours to obtain the finished catalyst for the catalytic cracking light gasoline fraction. Finished catalyst P 2 O 5 And Ce (Ce) 2 O 3 The content was 2% and 1.5%, respectively.
In this embodiment, the reactor of the heavy gasoline fraction aromatization apparatus is one selected from a fixed bed reactor, a moving bed reactor, and a fluidized bed reactor; more preferably, it is a fixed bed reactor or a moving bed reactor.
In this embodiment, the main process parameters of the aromatization apparatus are: the reaction temperature is 450-550 ℃, the system pressure is 0-2MPa, and the feeding airspeed is 0.3-3h -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the reaction temperature is 480-530 ℃, the system pressure is 0.3-1.3MPa, and the feeding airspeed is 0.5-1h -1 . It will be appreciated that the reaction temperature in this embodiment may be any specific value of 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃ or any value in the range of 450-550 ℃; the system pressure may be any specific value of 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa or any value in the range of 0-2 MPa; feeding inThe space velocity of the material can be 0.5h -1 、0.6h -1 、0.7h -1 、0.8h -1 、0.9h -1 、1h -1 Any specific value of (2) is alternatively 0.3-3h -1 Any number within the range.
In this example, the catalyst used in the aromatization treatment was constituted as follows: the active component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And ZnO; further, the mass content of each component in the catalyst is as follows: 50-90% HZSM-5 molecular sieve, 10-50% catalyst carrier, 1-5% P 2 O 5 1-5% ZnO; more preferably, the mass content of each component in the catalyst is as follows: 65-80% ZSM-5 molecular sieve, 20-35% catalyst carrier, 1-2%P 2 O 5 2.5-3.5% ZnO. It will be appreciated that the HZSM-5 molecular sieve may have a mass fraction of any particular value of 65%, 70%, 75%, 80% or any value in the range of 50-90% based on 100% total; catalyst support Al 2 O 3 The mass ratio of (2) may be any specific value of 20%, 25%, 30%, 35% or any value in the range of 10-50%; p (P) 2 O 5 The mass ratio of (2) may be any specific value in 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% or any value in the range of 1-5%; ce (Ce) 2 O 3 The mass ratio of (c) may be any specific value of 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5% or any value in the range of 1 to 5%.
In the embodiment, the silicon-aluminum ratio of the HZSM-5 molecular sieve in the aromatization catalyst is 30-90; more preferably 38-60. It will be appreciated that the HZSM-5 molecular sieve may have a silica to alumina ratio of any particular value of 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60 or any value in the range of 30-90.
In this embodiment, a method for preparing the aromatization catalyst is provided: mixing HZSM-5 molecular sieve 500-900kg with silicon-aluminum ratio of 30-90 and pseudo-boehmite 200-500kg, adding dilute nitric acid and lemonMixing citric acid and herba Setariae viridis powder, rolling, extruding, drying at 100-200deg.C for 0.5-12 hr, and roasting at 500-700deg.C for 0.5-12 hr; the roasted catalyst is subjected to isovolumetric saturated impregnation by using an ammonium dihydrogen phosphate aqueous solution and a zinc nitrate aqueous solution, and finally the impregnated catalyst is dried for 5 hours at 100-250 ℃ and then roasted for 0.5-12 hours at 500-700 ℃ to obtain the treated heavy gasoline fraction and C 5 + Aromatization finished catalyst of component mixture, finished catalyst P 2 O 5 And ZnO content is 1-5% and 1-5%, respectively. Obviously, the catalytic cracking catalyst is not limited to the specific limitation of the above process parameters, for example, the addition amount of the raw materials such as HZSM-5 molecular sieve, pseudo-boehmite, ammonium dihydrogen phosphate aqueous solution, zinc nitrate aqueous solution and the like can be adjusted; for example, the drying temperature after extrusion molding can be 135 ℃, 145 ℃, 155 ℃, 165 ℃ and the like, and the drying time can be 3.5h, 4h, 4.5h, 5.5h, 6h, 6.5h and the like; the baking temperature after extrusion molding and drying can be 580 ℃, 590 ℃, 610 ℃, 620 ℃ and the like, and the baking time can be 3.5h, 4h, 4.5h, 5.5h, 6h, 6.5h and the like; the drying temperature of the impregnated catalyst can be 135 ℃, 145 ℃, 155 ℃, 165 ℃ and the like, and the drying time can be 3.5 hours, 4 hours, 4.5 hours, 5.5 hours, 6 hours, 6.5 hours and the like; the final roasting temperature can be 580 ℃, 590 ℃, 610 ℃, 620 ℃ and the like, and the roasting time can be 3.5h, 4h, 4.5h, 5.5h, 6h, 6.5h and the like.
As a more specific description, the present embodiment provides a specific preparation method of the above aromatization catalyst: mixing 750kg of HZSM-5 molecular sieve with a silicon-aluminum ratio of 45 and 390kg of pseudo-boehmite uniformly, adding dilute nitric acid, citric acid and sesbania powder, mixing, rolling and extruding to form strips, drying at 150 ℃ for 5 hours, and roasting at 600 ℃ for 5 hours; the roasted catalyst is subjected to isovolumetric saturated impregnation by using an ammonium dihydrogen phosphate aqueous solution and a zinc nitrate aqueous solution, and finally the impregnated catalyst is dried for 5 hours at 150 ℃ and then is roasted for 5 hours at 600 ℃ to obtain the treated heavy gasoline fraction and C 5 + Aromatization finished catalyst of component mixture, finished catalyst P 2 O 5 And ZnO contents of 1% and 3%, respectively.
The following describes a method for producing olefins and aromatics from catalytically cracked gasoline according to the present invention with reference to specific examples.
Example 1
A process method for producing olefin and aromatic hydrocarbon by catalytically cracking gasoline comprises the following steps: sending the catalytic cracking gasoline into an atmospheric distillation device for separation to obtain a light gasoline fraction and a heavy gasoline fraction; then, the light gasoline fraction is sent to a catalytic cracking device for treatment to obtain C 1 -C 4 Component and C 5 + A component separating said heavy gasoline fraction and said C 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon.
In this particular example, the composition of the catalytically cracked gasoline is shown in table 2 below:
TABLE 2 catalytic cracking gasoline principal Properties
In this example, the main properties of the light gasoline and the heavy gasoline separated by atmospheric distillation are shown in tables 3 and 4. Wherein the light gasoline yield is 47.5%, and the heavy gasoline yield is 52.5%.
TABLE 3 catalytic cracking light gasoline fraction principal Properties
| Density, g/cm 3 | 0.68 |
| Sulfur, w% | 0.0025 |
| Distillation range, DEG C | |
| Initial point of distillation | 36 |
| 50％ | 65 |
| End point of distillation | 88 |
| Group composition, v% | |
| Aromatic hydrocarbons | 1.50 |
| Olefins | 64.1 |
| Alkanes | 35.4 |
TABLE 4 catalytic cracking heavy light gasoline fraction principal Properties
| Density, g/cm 3 | 0.75 |
| Sulfur, w% | 0.019 |
| Distillation range, DEG C | |
| Initial point of distillation | 83 |
| 50％ | 142 |
| End point of distillation | 208 |
| Group composition, v% | |
| Aromatic hydrocarbons | 42.6 |
| Olefins | 27.7 |
| Alkanes | 29.7 |
In the specific embodiment, the catalytic cracking of the catalytic cracking light gasoline utilizes the fluidized bed process technology, and the process operation conditions are as follows: the reaction temperature is 630 ℃, the water-oil ratio is 0.1, and C 4 The remilling ratio of the components is 0.2 (remilling C 4 Ratio of components to catalytically cracked light gasoline feed), the space velocity of the feed was 2h -1 。
In this embodiment, the preparation method of the catalytic cracking catalyst includes: 710kg of aluminum sol (Al) 2 O 3 21% of the content) by slowly adding water and pseudo-thin while stirring530kg of diaspore, and 500kg of HZSM-5 molecular sieve with the silicon-aluminum ratio of 120 is slowly added while stirring for 2 hours; then stirring for 5 hours, spray drying and forming under the conditions of a hearth temperature of 400 ℃, an outlet temperature of 200 ℃ and a spray pressure of 4MPa, and then roasting for 5 hours at 600 ℃; and (3) carrying out equal volume saturated impregnation on the roasted catalyst by using an ammonium dihydrogen phosphate aqueous solution and a cerium nitrate aqueous solution, drying the impregnated catalyst at 150 ℃ for 5 hours, and roasting at 600 ℃ for 5 hours to obtain the catalytic cracking gasoline catalytic cracking finished catalyst. Finished catalyst P 2 O 5 And Ce (Ce) 2 O 3 The content was 2% and 1.5%, respectively. The distribution of the catalytic cracking products of the catalytic cracking light gasoline is shown in table 5.
TABLE 5 distribution of catalytically cracked light gasoline, percent
| Dry gas (ethylene) | 16.7(13.2) |
| Propylene | 29.5 |
| Liquefied gas | 15.6 |
| C 5 + | 38.2 |
Note that: the dry gas (ethylene) is the first dry gas.
In this embodiment, the preparation method of the aromatization catalyst comprises: mixing HZSM-5 molecular sieve of 45 silicon-aluminum ratio 750kg and pseudo-boehmite 390kg, adding dilute nitric acid 3%, citric acid 3% and sesbania powder 3%, mixing, rolling, extruding, and moldingDrying at 150deg.C for 5 hr, and roasting at 600deg.C for 5 hr; the roasted catalyst is subjected to isovolumetric saturated impregnation by using an ammonium dihydrogen phosphate aqueous solution and a zinc nitrate aqueous solution, and finally the impregnated catalyst wire is dried for 5 hours at 150 ℃ and then is roasted for 5 hours at 600 ℃ to obtain the catalytic cracking C 5 + Product and part C 4 Aromatization of the component mixture to form the finished catalyst. P in the finished catalyst 2 O 5 And ZnO contents of 1% and 3%, respectively.
In this example, heavy gasoline and C are catalytically cracked 5 + The mixture aromatization of the product utilizes a fixed bed process, and the process operation conditions are as follows: the reaction temperature is 510 ℃ and the feeding space velocity is 0.5h -1 The reaction pressure was 0.5MPa. Catalytic cracking heavy gasoline and catalytic cracking C 5 + The product mixture aromatization product distribution is shown in Table 6 and the mixed aromatic composition is shown in Table 7.
TABLE 6 catalytic cracking heavy gasoline and catalytic cracking C 5 + Mixture of products aromatization product distribution,%
| Dry gas × | 9.7 |
| Liquefied gas | 22.0 |
| Mixed aromatic hydrocarbons | 68.2 |
Note that: dry gas is the second dry gas.
TABLE 7 mixing aromatic major Properties
By integrating the above processes, the total material balance of directly producing light olefins and light aromatics from the catalytically cracked gasoline can be calculated as shown in table 8.
TABLE 8 total Material balance for direct production of light olefins and light aromatics from catalytically cracked gasoline
| Project | Quantity of |
| Dry gas (ethylene) | 7.9(6.3) |
| Dry gas × | 6.9 |
| Propylene | 14.1 |
| Liquefied gas | 22.9 |
| Mixed aromatic hydrocarbons | 48.2 |
In this embodiment, the dry gas (ethylene) obtained from the catalytic cracking of the catalytically cracked light gasoline is rich in ethylene, and the ethylene in the dry gas can be directly utilized for productionChemicals (such as ethylbenzene production) may also be enriched to pure ethylene as a chemical raw material; catalytic cracking C of catalytic cracking heavy gasoline and catalytic cracking light gasoline 5 + The dry gas obtained by aromatizing the mixture of the products is basically free of ethylene and can be used as fuel gas or separated ethane for preparing ethylene by steam cracking; the propylene desulfurized refined propylene obtained by gas separation of the catalytic cracking light gasoline catalytic cracking product can be directly used in chemical industry; the main components of the liquefied gas obtained by catalytic cracking of the catalytic cracking light gasoline and the liquefied gas obtained in the aromatization process are propane and butane, which are high-quality raw materials for preparing ethylene by steam cracking; the concentration of the mixed aromatic hydrocarbon obtained by aromatizing the catalytic cracking mixture of the catalytic cracking heavy gasoline and the catalytic cracking light gasoline is as high as 93.8 percent, and the qualified light aromatic hydrocarbon (BTX) can be obtained by further separation and conversion.
The catalytic cracking gasoline is separated into light and heavy components, and then is subjected to catalytic cracking and aromatization respectively, so that chemical basic raw materials such as ethylene, propylene, benzene, toluene, xylene and the like can be directly produced, and gas byproducts such as dry gas and liquefied gas are high-quality raw materials for preparing ethylene by steam cracking.
In a word, through the technological method provided by the embodiment, olefin and aromatic hydrocarbon can be produced to the greatest extent, and the technological process is novel and has good processing flexibility.
The technical idea of the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (14)
1. A process for producing olefins and aromatics from catalytically cracked gasoline, comprising: sending the catalytic cracking gasoline into an atmospheric distillation device for separation to obtain a light gasoline fraction and a heavy gasoline fraction; then, the light gasoline fraction is sent to a catalytic cracking device for treatmentObtaining C 1 -C 4 Component and C 5 + A component separating said heavy gasoline fraction and said C 5 + The components are mixed and then sent to an aromatization device for treatment, so as to obtain second dry gas, liquefied gas and mixed aromatic hydrocarbon.
2. The process for producing olefins and aromatics from catalytically cracked gasoline according to claim 1, wherein said C 1 -C 4 The components are separated to obtain first dry gas, propylene, propane and C 4 The components are as follows.
3. A process for producing olefins and aromatics from catalytically cracked gasoline as claimed in claim 2, wherein C 1 -C 4 C obtained by separating components 4 One part of the components is returned to the catalytic cracking device for recycling, and the other part is directly used as liquefied petroleum gas products after being mixed with propane.
4. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 1, wherein the separation temperature of light gasoline and heavy gasoline in an atmospheric distillation unit is 65-95 ℃.
5. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 1, wherein said catalytic cracker is one of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.
6. The process for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline as claimed in claim 5, wherein the reaction temperature of the catalytic cracking device is 450-750 ℃, the system pressure is 0-1MPa, and the feeding airspeed is 0.5-5h -1 。
7. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 5 or 6, wherein the catalyst in the catalytic cracking unit is constituted by: living bodyThe sex component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And Ce (Ce) 2 O 3 。
8. The process for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline as claimed in claim 7, wherein the mass content of each component of the catalyst in the catalytic cracking device is: 40-80% HZSM-5 molecular sieve, 20-60% catalyst carrier, 1-5% P 2 O 5 、1-5％Ce 2 O 3 。
9. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 8, wherein the silica-alumina ratio of HZSM-5 molecular sieve in the catalytic cracking catalyst is 60-150.
10. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 1, wherein said reactor of said aromatization device is one selected from the group consisting of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.
11. The process for producing olefin and aromatic hydrocarbon by catalytic cracking gasoline as claimed in claim 10, wherein the reaction temperature of the aromatization device is 450-550 ℃, the system pressure is 0-2MPa, and the feeding airspeed is 0.3-3h -1 。
12. The process for producing olefins and aromatics from catalytically cracked gasoline according to claim 10 or 11, wherein the catalyst in the aromatization unit is constituted by: the active component is HZSM-5 molecular sieve, and the catalyst carrier is Al 2 O 3 The modified substance is P 2 O 5 And ZnO.
13. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 12, wherein the mass content of each component of the catalyst in the aromatization apparatus is: 50-90% HZSM-5 minSub-sieve, 10-50% catalyst carrier, 1-5% P 2 O 5 、1-5％ZnO。
14. The process for producing olefins and aromatics by catalytic cracking of gasoline according to claim 12 or 13, wherein the ratio of silica to alumina of HZSM-5 molecular sieve in aromatization catalyst is 30-90.
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