CN113620767B - Method and reaction system for producing low-carbon olefin and aromatic hydrocarbon - Google Patents
Method and reaction system for producing low-carbon olefin and aromatic hydrocarbon Download PDFInfo
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- CN113620767B CN113620767B CN202010383178.4A CN202010383178A CN113620767B CN 113620767 B CN113620767 B CN 113620767B CN 202010383178 A CN202010383178 A CN 202010383178A CN 113620767 B CN113620767 B CN 113620767B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 57
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 50
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000926 separation method Methods 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 46
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 33
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 29
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 125
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000001294 propane Substances 0.000 claims description 33
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 32
- 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 29
- 239000003502 gasoline Substances 0.000 claims description 28
- 239000002808 molecular sieve Substances 0.000 claims description 28
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 25
- 238000004230 steam cracking Methods 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002283 diesel fuel Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 42
- 238000005336 cracking Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102000039963 DCC family Human genes 0.000 description 1
- 108091069213 DCC family Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- LFKIGTZUWPXSIH-UHFFFAOYSA-N but-1-ene;2-methylprop-1-ene Chemical compound CCC=C.CC(C)=C LFKIGTZUWPXSIH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XLNZHTHIPQGEMX-UHFFFAOYSA-N ethane propane Chemical compound CCC.CCC.CC.CC XLNZHTHIPQGEMX-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004947 monocyclic arenes Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method and a reaction system for producing light olefins and aromatic hydrocarbons, comprising: (1) Introducing the four components of raw materials into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing the oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, and separating ethylene, propylene, aromatic hydrocarbon products and a first four components of the separated reaction oil gas by a separation system; (2) The first carbon four component enters an aromatization reactor to contact and react with an aromatization catalyst, and the reaction product is separated into ethylene, propylene and aromatic hydrocarbon products through a separation system; (3) The second four-carbon component enters an alkane dehydrogenation reactor, contacts a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor. The method provided by the invention has high yield of ethylene, propylene and aromatic hydrocarbon and low energy consumption.
Description
Technical Field
The invention relates to a method and a reaction system for producing chemical raw materials from petroleum raw materials, in particular to a method and a reaction system for producing ethylene, propylene and aromatic hydrocarbon from light hydrocarbon.
Technical Field
Ethylene, propylene and BTX aromatics are growing in demand annually as a large number of basic chemical feedstocks. Catalytic cracking, which is used as a device for producing gasoline by processing heavy oil, also produces a large amount of propylene as a byproduct, and is a main supplementary source in the propylene market. Wherein deep catalytic cracking (such as DCC process) using more shape selective molecular sieve (ZSM-5) as active center can produce propylene in large quantity and by-produce certain propylene and BTX aromatic hydrocarbon. At present, wax oil or hydrogenated wax oil is generally adopted in the process, and a small amount of residual oil or paraffin-based atmospheric residual oil is doped as a raw material.
The technology for preparing propylene from liquefied gas rich in olefin uses liquefied gas with lower added value as raw material, and uses the cracking reaction of carbon tetraolefin in liquefied gas under the action of catalyst to produce propylene, ethylene and high-octane aromatic hydrocarbon-rich gasoline component with high added value, for example, in the DCC family technology, C4 olefin is returned into catalytic cracking device to make cyclic re-cracking so as to produce ethylene and propylene. Meanwhile, ethanol gasoline is promoted nationwide by 2020, etherified C4 or etherified light gasoline products are limited to be added into finished gasoline, a large number of C4 etherification devices are idle, and the reprocessing and the utilization of C4 olefins are paid attention to.
CN104878A discloses a process for producing low-carbon olefin, which uses gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materialsRaw materials, using a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a fluidized bed or moving bed reactor is adopted; the operation conditions are that the pressure is 150 kPa-300 kPa, the reaction temperature is 550-650 ℃, and the airspeed is 0.2-20hr -1 And the agent-oil ratio is 2-12. The method has high reaction temperature, more methane byproducts and generates a large amount of unusable carbon four and diesel oil.
CN1034586a discloses a method for producing low-carbon olefin from hydrocarbon oil, which uses gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials, and uses Y-type molecular sieve and phosphorus-containing ZSM-5 molecular sieve as active centers; a fluidized bed or riser reactor is adopted; the operation conditions are that the pressure is 120 kPa-400 kPa, the reaction temperature is 480-680 ℃, the residence time is 0.1-6 seconds, the catalyst-to-oil ratio is 4-20, and the atomized water vapor accounts for 1-50% of the weight of the raw material. The method has similar problems as CN104878 in that the reaction temperature is high, methane byproducts are more, and a large amount of unusable carbon four and diesel oil are produced despite the modification of the catalyst.
CN1056595a discloses a process for low-carbon olefin production using multistage feed from ethane to resid as feedstock. The method uses an alkaline earth metal-containing molecular sieve as an active center; a riser reactor is adopted; the operation conditions are 130kPa to 400kPa of pressure, 600 ℃ to 900 ℃ of reaction temperature, 0.1 to 6 seconds of residence time and 5 to 100 of catalyst-oil ratio, and the cracking of the multi-stage feed is carried out from high to low according to different cracking difficulties. Although the method solves the problems of byproducts such as carbon four, the method also has the problems of more methane and coke byproducts for the raw materials with poor processing property,
CN102337148A discloses a method for producing low-carbon olefin by using gasoline rich in four to eight carbon atoms as raw material. The method uses Y-type molecular sieve and ZSM-5 molecular sieve as active centers; a riser reactor and a fluidized bed reactor are adopted; the operation conditions are that the pressure is 150 kPa-300 kPa, the reaction temperature is 480-680 ℃, the retention time of the riser is 1-5 seconds, and the space velocity of the fluidized bed is 0.2-30hr -1 The agent-oil ratio is 8-40. The method can not solve the accumulation of alkane components despite the cyclic utilization of the C four-to C eight-alkene.
CN101362961A discloses a process for preparing hydrocarbon at 160-270 deg.C from fractionA method for preparing low-carbon olefin and aromatic hydrocarbon. The method uses Y-type molecular sieve and ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the operation conditions are that the pressure is 100 kPa-1000 kPa, the reaction temperature is 450-750 ℃, and the airspeed is 1-150hr -1 The agent-oil ratio is 1-150. The method solves the problem of partial diesel oil outlet.
CN 1667089a discloses a method for producing low-carbon olefin by using gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials. The method comprises the steps of hydrotreating a raw material and a circulating material flow, and then feeding the material flows into a catalytic cracking reactor. Wherein the gas recycle is ethane, propane and carbon four. The liquid circulation feed is C5-C6, heavy gasoline aromatic raffinate oil, LCO, HCO and slurry oil. Although the method solves the outlet of most byproducts, the method can not solve the accumulation problem of alkane components and polycyclic aromatic hydrocarbon components.
In the method, the problems of high circulating ratio of the four carbon components, low propylene yield and high energy consumption exist.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problems of high circulation proportion of carbon four components, low propylene yield and high energy consumption in the prior art, and provide a method for producing low-carbon olefin and aromatic hydrocarbon with high product yield.
The second technical problem to be solved by the invention is to provide a catalytic conversion reaction system for producing low-carbon olefin and aromatic hydrocarbon.
A process for producing light olefins and aromatics comprising:
(1) Introducing the four components of raw materials into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas, gasoline, diesel oil and slurry oil from the separated reaction oil gas by a separation system, and further separating propylene, propane and a first four components of the liquefied gas;
(2) The separated first carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, propylene, propane and the second carbon four components are further separated from the liquefied gas, and aromatic hydrocarbon is further separated from the gasoline rich in aromatic hydrocarbon;
(3) The second four-carbon component enters an alkane dehydrogenation reactor, contacts a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor.
A reaction system for producing light olefins and aromatic hydrocarbons, comprising a reaction device, a catalyst and a reactant stream; the reaction device comprises a catalytic cracking reactor, a regenerator, a first oil-gas separation system, a second oil-gas separation system, an aromatization reactor and an alkane dehydrogenation reactor which are communicated in sequence; the regeneration agent outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and gas-solid separation equipment, the spent agent outlet of the gas-solid separation equipment is communicated with the regenerator, the oil-gas outlet of the gas-solid separation equipment is communicated with the first oil-gas separation system, the C4 outlet of the first oil-gas separation system is communicated with the aromatization reactor, the outlet of the aromatization reactor is communicated with a second oil-gas separation system, the C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and the product outlet of the dehydrogenation reactor is communicated with the catalytic cracking reactor; the catalytic cracking catalyst circularly flows in the catalytic cracking reactor and the regenerator, the aromatization catalyst is filled in the aromatization reactor, and light hydrocarbon raw materials are introduced through a raw material inlet of the catalytic cracking reactor and react in the reaction device.
The method and the reaction system for producing the low-carbon olefin and the aromatic hydrocarbon have the beneficial effects that:
in the method for producing the low-carbon olefin by recycling the four-carbon fraction back to the catalytic cracking device, the reaction speed of the four-carbon alkane is obviously slower than that of the four-carbon olefin, the conversion rate of the four-carbon olefin is higher in the process of mixing the four-carbon fraction in the catalytic cracking reactor, the conversion rate of the four-carbon alkane is extremely low, and the circulating material flow of the four-carbon alkane is continuously accumulated in the process of recycling the four-carbon component. In this case, if the carbon four recycle ratio is not increased, the propylene yield is lowered due to the reduction of the olefin content in the carbon four. If the carbon four cycle ratio is increased, the energy consumption is greatly increased.
The method solves the problem of accumulation of the carbon tetraalkylalkanes in the carbon tetracycling material flow, and greatly reduces the energy consumption and the operation cost of the carbon tetracycling. And the yield of ethylene, propylene and aromatic hydrocarbon is greatly increased, the ethylene, propylene and aromatic hydrocarbon can be produced in the largest quantity, and more high-quality cracking raw materials of ethane, propane and n-butane are provided for steam cracking. The method provided by the invention can also reduce the heat-taking load of the aromatization device and reduce the energy consumption of the aromatization device.
Drawings
FIG. 1 is a schematic flow chart of the process for producing light olefins and aromatics provided by the invention.
FIG. 2 is a schematic flow chart of the method for producing ethylene and propylene in comparative examples 1 and 2.
Wherein:
1-a catalytic cracking reactor; a 2-aromatization reactor; a 3-alkane dehydrogenation reactor; 4-regenerator; 5-a first oil-gas separation system; 6-a second oil-gas separation system; 8-regenerating the catalyst chute; 9-a spent catalyst chute; 10-stripping section; 11-a settler; a 32-propane pyrolysis furnace; 33-ethane pyrolysis furnace; 35-a gas separation device; 31. 34-dry gas line, 37-ethane line; 7-a raw material pipeline; 12. 13, 14, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 36, 38-line.
Detailed Description
The following describes specific embodiments of the present invention:
the method for producing the low-carbon olefin and the aromatic hydrocarbon provided by the invention comprises the following steps:
(1) Introducing the four components of raw materials into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas, gasoline, diesel oil and slurry oil from the separated reaction oil gas by a separation system, and further separating propylene, propane and a first four components of the liquefied gas;
(2) The separated first carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, propylene, propane and the second carbon four components are further separated from the liquefied gas, and aromatic hydrocarbon is further separated from the gasoline rich in aromatic hydrocarbon;
(3) The second four-carbon component enters an alkane dehydrogenation reactor, contacts a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor.
Preferably, the method further comprises the step (4): and (3) separating propane from the dry gas in the steps (1) and (2) to obtain ethane, and feeding the ethane into a steam cracking furnace for steam cracking to generate ethylene and propylene.
In the method provided by the invention, the low-carbon olefin is ethylene and propylene.
Preferably, the feed carbon four component is from a catalytic cracking unit and contains carbon tetraolefins and carbon tetraalkanes, wherein the olefin content in the feed carbon four component is more than 20wt%. Preferably, the olefin content in the carbon four component of the feedstock is 40wt% to 80%.
In the method provided by the invention, the catalyst in the step (1) is a catalytic cracking catalyst, and comprises an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein the content of the MFI structure molecular sieve is 5-60 wt%, preferably 10-50 wt%, the content of the Y-type molecular sieve is 1-40 wt%, preferably 1-30 wt%, the content of the clay is 10-70 wt%, preferably 15-45 wt%, and the content of the binder is 5-40 wt%, preferably 5-30 wt%, based on the total weight of the catalyst.
In the method provided by the invention, the catalytic cracking reactor is one or a combination of a riser reactor, a turbulent bed reactor and a rapid bed reactor; the operating conditions of the catalytic cracking reactor were: the average temperature is 550-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1 。
In the method provided by the invention, the gas-solid separation in the step (1) is carried out in a settler, a cyclone gas-solid separator is adopted to separate the catalyst and the reaction oil gas, and the separated catalyst is stripped in a stripper.
The method provided by the invention is characterized in that the aromatization reactor is a fixed bed reactor.
The method provided by the invention is characterized in that the aromatization catalyst contains a molecular sieve, a metal active component and a heat-resistant inorganic oxide carrier, wherein the metal active component is selected from one or more of rare earth elements and VIB, VIII, IIB, VIIB elements, and the heat-resistant inorganic oxide is preferably silicon oxide and aluminum oxide.
In the method provided by the invention, the operating conditions of the aromatization reactor are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 0.20-2.0 MPa, and the reaction space velocity is 0.2-2 h -1 。
In the method provided by the invention, the alkane dehydrogenation reactor is a fixed bed reactor; the operation conditions are that the reaction temperature is 550-650 ℃, the reaction pressure is 0.10-0.5 MPa, and the reaction space velocity is 0.2-2 h -1 。
The dehydrogenation catalyst contains a molecular sieve, one or more metal active components and a heat-resistant inorganic oxide carrier, wherein the metal active components are selected from one or more of rare earth elements, IA, IIA, VIB and VIII, IB, VIIB elements, and the heat-resistant inorganic oxide carrier is silicon oxide and aluminum oxide.
Step (4) adopts a propane steam cracking furnace and an ethane steam cracking furnace or adopts an ethane-propane cracking furnace; preferably, a propane steam cracker and an ethane steam cracker are used. The steam cracking operation condition is that the reaction temperature is 780-850 ℃ and the residence time is 0.01-3 seconds.
In the method provided by the invention, two oil-gas separation systems are adopted in the steps (1) and (2). The separation system comprises a fractionating tower, an absorption stabilization system and a gas separation device, specifically, the separated oil gas enters the catalytic cracking fractionating tower, the product below the gasoline obtained at the top of the fractionating tower enters the absorption stabilization system, the product gasoline separated by the stabilization system, dry gas and liquefied gas enter the gas separation device, and propylene, propane and four carbon components are separated. The dry gas enters a split separation device to separate ethylene, ethane and other gases.
The arene obtained in the step (2) is C6 to C10 monocyclic arene.
In the method provided by the invention, the raw material carbon four components refer to C4 components produced by a catalytic cracking device, the catalytic cracking device is used for contacting heavy oil raw materials with a catalytic cracking catalyst, and carrying out a cracking reaction under a catalytic cracking condition to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil, wherein the liquefied gas is further separated to obtain the C4 components. The heavy oil raw material is selected from one or a mixture of more than one of wax oil and atmospheric residue vacuum residue, or other organic compounds or hydrocarbons with carbon number more than 16. The catalytic cracking catalyst comprises an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein the content of the MFI structure molecular sieve is 5-60 wt%, preferably 10-50 wt%, the content of the Y-type molecular sieve is 1-40 wt%, preferably 1-30 wt%, the content of the clay is 10-70 wt%, preferably 15-45 wt%, and the content of the binder is 5-40 wt%, preferably 5-35 wt%, based on the total weight of the catalyst.
The operating conditions of the reactor in the catalytic cracking device are as follows: the average temperature is 500-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1 。
In the method provided by the invention, the same gas separation device is adopted for dry gas separation in the step (4), and the gas separation device comprises a rectifying tower and auxiliary equipment.
In the method provided by the invention, a part of the C4 component separated by the first oil-gas separation system is introduced into the aromatization reactor, and the other part of the C4 component is returned to the catalytic cracking reactor as circulating C4 to continue the reaction, and the rest of the C4 component can be thrown out as a C four product. And a C4 outlet of the first oil-gas separation system is respectively communicated with the aromatization reactor, the catalytic cracking reactor and the carbon four product pipeline leading-out device.
And part of the C4 component separated by the second oil-gas separation system is introduced into the alkane dehydrogenation reactor, and the other part of the C4 component can be used as a carbon four product to be thrown outwards. And a C4 outlet of the second oil-gas separation system is respectively communicated with the alkane dehydrogenation reactor and the carbon four product pipeline leading-out device.
The reaction product of the alkane dehydrogenation reactor can be partially thrown outside besides returning to the catalytic cracking reactor to continue the reaction. The product outlet of the alkane dehydrogenation reactor is also communicated with a carbon four product pipeline leading-out device.
A reaction system for producing light olefins and aromatic hydrocarbons, comprising a reaction device, a catalyst and a reactant stream; the reaction device comprises a catalytic cracking reactor, a regenerator, a first oil-gas separation system, a second oil-gas separation system, an aromatization reactor and an alkane dehydrogenation reactor which are communicated in sequence; the regeneration agent outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and gas-solid separation equipment, the spent agent outlet of the gas-solid separation equipment is communicated with the regenerator, the oil-gas outlet of the gas-solid separation equipment is communicated with the first oil-gas separation system, the C4 outlet of the first oil-gas separation system is communicated with the aromatization reactor, the outlet of the aromatization reactor is communicated with the second oil-gas separation system, the C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and the product outlet of the alkane dehydrogenation reactor is communicated with the catalytic cracking reactor; the catalytic cracking catalyst circularly flows in the catalytic cracking reactor and the regenerator, the aromatization catalyst is filled in the aromatization reactor, and the reactant flow is introduced through the raw material inlet of the catalytic cracking reactor and reacts in the reaction device.
Preferably, the reaction device further comprises a gas separation device and a steam cracking furnace; the dry gas outlets of the first and second oil-gas separation systems are connected with a gas separation device, and the ethane outlet of the gas separation device is communicated with an ethane steam cracking furnace. The propane outlets of the first and second oil-gas separation systems are communicated with a propane steam cracking furnace.
Preferably, the catalytic cracking reactor is a riser reactor, the aromatization reactor is a fixed bed reactor, and the alkane dehydrogenation reactor is a fixed bed reactor.
The regenerator is a type of regenerator in the art that uses air or air-mixed oxygen-enriched gas to react with coke on the spent catalyst, burns the coke off the spent catalyst to restore the activity of the spent catalyst, known as regenerated catalyst, and raises the catalyst temperature to 600 to 760 ℃ in order to return the reactor to bring heat and catalytic media to the reaction.
In the method and the reaction system for producing the low-carbon olefin and the aromatic hydrocarbon, the product outlets of the catalytic cracking reactor and the aromatization reactor can respectively adopt respective oil-gas separation systems, and can also share one set of oil-gas separation system. The oil-gas separation system can adopt one or more of a fractionating tower, a rectifying tower, an absorbing tower and a desorber.
FIG. 1 is a schematic flow chart of the method provided by the invention, as shown in FIG. 1, a carbon four raw material enters a catalytic cracking reactor 1 through a pipeline 7 after being preheated and reacts with a thermal regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined pipe 8 in a contact way, the catalytic cracking reactor 1 is a riser reactor, generated oil gas and catalyst enter a settler 11, a gas-solid separation device is arranged in the settler 11, the oil gas and the catalyst in the settler 11 are separated, the separated catalyst with carbon enters a stripping section 10 for stripping, enters the regenerator 4 through the catalyst inclined pipe 9, the coke on the catalyst is burned off by air through a pipeline 25 in the regenerator 4 to restore the activity, and then enters the bottom of the catalytic cracking reactor 1 through the regenerated catalyst inclined pipe 8 for recycling. The separated oil and gas enters the first oil and gas separation system 5 through a pipeline 12. The gasoline of the first oil-gas separation system is led out through a pipeline 15, the diesel oil is led out through a pipeline 16, the slurry oil is led out through a pipeline 26, the propylene is led out through a pipeline 27, and the propane is led out through a pipeline 13 and enters a propane cracking furnace 32; the dry gas enters a gas separation device 35 through a pipeline 31, the gas separation device consists of a plurality of rectifying towers, H2-CH4 is led out through a pipeline 28 after separation, ethylene is led out through a pipeline 36, and ethane is led out through a pipeline 37 and enters an ethane cracking furnace 33. The first carbon four component separated by the first oil-gas separation system is led out through a pipeline 14 and enters the aromatization reactor 2, and a part of the first carbon four component is recycled to the catalytic cracking reactor through a pipeline 40.
The aromatization reactor is a fixed bed reactor, in the aromatization reactor, the second carbon four component and the aromatization catalyst are in contact reaction, the reaction product enters a second oil-gas separation system through a pipeline 17, after separation, the obtained aromatic hydrocarbon-rich gasoline is led out through a pipeline 20, propylene is led out through a pipeline 18, propane is led out through a pipeline 21 and enters a propane cracking furnace 32, dry gas is led out through a pipeline 34 and enters a gas separation device 35, and the second carbon four component is led out through a pipeline 19 and enters an alkane dehydrogenation reactor 3.
In the alkane dehydrogenation reactor 3, the carbon four component is contacted and reacted with an alkane dehydrogenation catalyst, wherein the carbon four alkane is dehydrogenated to form carbon four alkene, and the reaction product is returned to the catalytic cracking reactor for reaction through a pipeline 24.
The propane separated by the first oil-gas separation system 5 enters the propane steam cracking furnace 32 through a pipeline 13, and the propane separated by the second oil-gas separation system 6 enters the propane steam cracking furnace 32 through a pipeline 21 to generate propylene and ethylene. Ethane separated by the gas separation unit 35 is fed via line 37 to an ethane cracker 33 to produce ethylene and propylene.
The effects of the method for producing light olefins and aromatic hydrocarbons and the reaction system provided by the present invention are described below by way of examples and comparative examples, but the present invention is not limited thereto.
In the comparative examples and examples, the C4 component used was taken from a catalytic cracking separation column of Shijia division of China petrochemical Co., ltd, and the properties are shown in Table 1. The catalyst used was DMMC-1 catalyst manufactured by catalyst division of China petrochemical Co., ltd. The properties are shown in Table 2. The adopted aromatization catalyst has the commodity brand of DLP-XA and is produced by Shandong Dazier chemical technology Co. The dehydrogenation catalyst used was commercially available under the trade designation BDH-5 from Daidan Michael company.
Comparative examples 1 to 2
Comparative examples 1-2A process for producing ethylene and propylene by C4-back catalytic cracking shown in figure 2 is carried out, as shown in figure 2, four components of raw materials enter a catalytic cracking riser reactor through a pipeline 7 after being preheated, contact with a thermal regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined pipe 8, catalytic cracking reaction is carried out, generated oil gas and catalyst flow upwards into a settler 11, gas-solid separation equipment is arranged in the settler 11, the reacted oil gas and catalyst are separated, the separated catalyst to be regenerated with carbon enters the regenerator 4 through a stripping section 10 after being stripped, coke on the catalyst to restore activity is burnt out through air from the pipeline 25 in the regenerator 4, and then the catalyst enters the bottom of the riser reactor through the inclined pipe 8 to circularly participate in the reaction. The separated oil and gas enters the first oil and gas separation system 5 through a pipeline 12. The first oil-gas separation system consists of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower, gasoline obtained after separation is led out through a pipeline 15, diesel oil is led out through a pipeline 16, slurry oil is led out through a pipeline 26, propylene is led out through a pipeline 27, and propane is led out through a pipeline 13 and enters a propane cracking furnace 32 to generate propylene 23 and ethylene 22. The resulting dry gas is withdrawn via line 31 and enters a gas separation unit 35 where the separated ethylene 28, other gases 36 and ethane 37 are withdrawn via line 37 and enter an ethane cracker 33 to produce ethylene and propylene. The four carbon components are led out through a pipeline 14, a part of four carbon components are returned to the catalytic cracking reactor through a pipeline 28, and the rest of four carbon components are taken as a product outlet device through a pipeline 20.
The reaction operating conditions of comparative examples 1 to 2 are shown in Table 3, and the product yields are shown in Table 4.
Examples 1 to 2
The embodiment 1-2 adopts a reaction flow shown in the attached figure 1, specifically, (1) raw material carbon four components are introduced into a catalytic cracking reactor to be in contact reaction with regenerated catalyst from the regenerator, oil gas and catalyst mixture obtained by the reaction enter a settler to be subjected to gas-solid separation, and the separated reaction oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and slurry oil by a separation system to further separate ethylene, propylene, aromatic hydrocarbon products and first carbon four components; (2) The first carbon four component enters an aromatization reactor to contact and react with an aromatization catalyst, and the reaction product is separated into dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon by a separation system, and ethylene, propylene, a second carbon four component and aromatic hydrocarbon products are further separated; (3) The second carbon four component enters an alkane dehydrogenation reactor, contacts a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor; (4) And (3) separating the dry gas and the liquefied gas in the steps (1) and (2) to obtain ethane and propane, and respectively feeding the ethane and propane into an ethane steam cracking furnace and a propane steam cracking furnace for steam cracking to generate ethylene and propylene.
The reaction operating conditions for examples 1-2 are shown in Table 3 and the product yields are shown in Table 4.
As can be seen from table 4, the carbon four recycle ratio (carbon four feed/raw material) of the examples of the carbon four raw material a and the carbon four raw material B was reduced by 0.2 and 0.3, respectively, compared to the comparative example, saving energy. In the product distribution, ethylene was increased by 0.76 and 1.49 percent, propylene was increased by 2.10 and 2.16 percent, and aromatic hydrocarbon (BTX) was increased by 10.47 and 17.11 percent, respectively.
TABLE 1 composition of C4 Components
| Raw materials | C4 component A | C4 component B |
| Isobutane | 26.18 | 38.75 |
| N-butane | 6.35 | 9.97 |
| Butene-1 | 10.01 | 11.18 |
| Isobutene (i-butene) | 28.90 | 12.92 |
| Maleic anhydride | 16.52 | 14.06 |
| Fumaric acid | 12.03 | 13.12 |
TABLE 2 catalytic cracking catalyst compositions and Properties
| RE 2 O 3 | 0.56 |
| Al 2 O 3 | 54 |
| Physical Properties | |
| Specific surface, m 2 /g | 100 |
| Pore volume, cm 3 /g | 0.176 |
| Micropore volume, cm 3 /g | 0.026 |
| Apparent density, g/cm 3 | 0.91 |
| Sieving,% of | |
| 0-20μm | 0.8 |
| 0-40μm | 10.4 |
| 0-80μm | 70.8 |
| 0-110μm | 88.5 |
| 0-149μm | 97.8 |
| >149μm | 2.2 |
| APS,μm | 64.3 |
| Micro-reactive, wt% (520 ℃ C.) | 55 |
TABLE 3 Table 3
| Project | Comparative example 1 | Example 1 | Comparative example 2 | Example 2 |
| Catalytic cracking reactor | ||||
| C4 raw material | C4 component A | C4 component A | C4 component B | C4 component B |
| Reaction pressure/MPa | 0.2 | 0.2 | 0.28 | 0.28 |
| Reaction temperature/. Degree.C | 620 | 620 | 650 | 650 |
| Regenerator temperature/°c | 690 | 690 | 710 | 710 |
| Ratio of agent to oil | 15 | 15 | 20 | 20 |
| Reaction space velocity/h -1 | 10 | 10 | 50 | 50 |
| Atomizing steam/% | 25 | 25 | 15 | 15 |
| Carbon four cycle ratio | 0.5 | 0.2 | 0.4 | 0.2 |
| Aromatization reactor | ||||
| Reaction pressure/MPa | / | 1.1 | / | 1.3 |
| Reaction temperature/. Degree.C | / | 380 | / | 420 |
| Reaction space velocity/h -1 | / | 1.0 | / | 1.3 |
| Alkane dehydrogenation reactor | ||||
| Reaction pressure/MPa | / | 0.3 | / | 0.3 |
| Reaction temperature/. Degree.C | / | 600 | / | 620 |
| Reaction space velocity/h -1 | / | 0.5 | / | 1.1 |
| Ethane cracking reactor | ||||
| Temperature/. Degree.C | 830 | 830 | 830 | 830 |
| pressure/MPa | 0.13 | 0.13 | 0.13 | 0.13 |
| Atomizing steam/% | 60 | 60 | 60 | 60 |
| Propane cracking reactor | ||||
| Temperature/. Degree.C | 815 | 815 | 815 | 815 |
| pressure/MPa | 0.13 | 0.13 | 0.13 | 0.13 |
| Atomizing steam/% | 60 | 60 | 60 | 60 |
TABLE 4 Table 4
| Example numbering | Comparative example1 | Example 1 | Comparative example 2 | Example 2 |
| Product yield | ||||
| H2-C2 | 5.77 | 8.12 | 7.94 | 9.38 |
| C3-C4 | 76.38 | 54.51 | 86.26 | 72.73 |
| C5+ gasoline | 13.51 | 31.61 | 3.04 | 14.27 |
| Diesel oil | 0.77 | 1.31 | 0.42 | 0.75 |
| Heavy oil | 0.02 | 0.30 | 0.12 | 0.29 |
| Coke | 3.36 | 3.64 | 2.02 | 2.19 |
| Ethylene | 3.47 | 4.96 | 3.99 | 4.75 |
| Propylene | 16.59 | 18.75 | 8.58 | 10.68 |
| BTX | 1.26 | 18.37 | 1.34 | 11.81 |
Claims (18)
1. A process for producing ethylene, propylene and aromatics comprising:
(1) Introducing the four components of raw materials into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas, gasoline, diesel oil and slurry oil from the separated reaction oil gas by a separation system, and further separating propylene, propane and a first four components of the liquefied gas;
(2) The separated first carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, propylene, propane and the second carbon four components are further separated from the liquefied gas, aromatic hydrocarbon is further separated from the gasoline rich in aromatic hydrocarbon, and the aromatization reaction temperature is 350-450 ℃;
(3) The second carbon four component enters an alkane dehydrogenation reactor, contacts a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor;
(4): separating propane from dry gas in the steps (1) and (2) to obtain ethane, and then feeding the ethane into a steam cracking furnace for steam cracking to generate ethylene and propylene;
the raw material carbon four component contains carbon tetraolefin and carbon tetraalkane, wherein the olefin content is more than 20wt%。
2. The process for producing ethylene, propylene and aromatics according to claim 1, wherein said feedstock carbon four components are from a catalytic cracker.
3. A process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein the olefin content in the carbon four component of the feedstock is 40wt%-80%。
4. The method for producing ethylene, propylene and aromatic hydrocarbon according to claim 1 or 2, wherein the catalyst in the step (1) is a catalytic cracking catalyst comprising an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, and the content of the MFI structure molecular sieve is 5 to 60 wt%, the content of the Y-type molecular sieve is 1 to 40wt%, the content of the clay is 10 to 70 wt%, and the content of the binder is 5 to 40wt%, based on the total weight of the catalyst.
5. The method for producing ethylene, propylene and aromatic hydrocarbon according to claim 4, wherein the catalyst in the step (1) is a catalytic cracking catalyst, the content of the MFI structure molecular sieve is 10 to 50% by weight, the content of the Y-type molecular sieve is 1 to 30% by weight, the content of the clay is 15 to 45% by weight, and the content of the binder is 5 to 30% by weight, based on the total weight of the catalyst.
6. The method for producing ethylene, propylene and aromatic hydrocarbon according to claim 1 or 2, wherein the catalytic cracking reactor is one or a combination of a riser reactor, a turbulent bed reactor and a fast bed reactor; the operating conditions of the catalytic cracking reactor were: the average temperature is 550-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1 。
7. The method for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein the aromatization catalyst comprises a molecular sieve, a metal active component and a refractory inorganic oxide support, and the metal active component is one or more selected from the group consisting of rare earth elements and VIB, VIII, IIB, VIIB elements.
8. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 7, wherein said refractory inorganic oxide is selected from the group consisting of silica and alumina.
9. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein said aromatization reactor is a fixed bed reactor.
10. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 9, wherein the operating conditions of said aromatization reactor are: the reaction pressure is 0.20-2.0 MPa, and the reaction space velocity is 0.2-2 h -1 。
11. According to the weightThe process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein the alkane dehydrogenation reactor is a fixed bed reactor; the operation conditions are that the reaction temperature is 550-650 ℃, the reaction pressure is 0.10-0.5 MPa, and the reaction space velocity is 0.2-2 h -1 。
12. The method of ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein the dehydrogenation catalyst comprises a molecular sieve and one or more metal active components selected from one or more of rare earth elements, group IA, IIA, VIB and VIII, IB, VIIB elements, and a refractory inorganic oxide support, which is silica and alumina.
13. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein step (4): the propane separated by the oil-gas separation system enters a propane steam cracking furnace, and the ethane separated from the dry gas enters an ethane steam cracking furnace to react to obtain ethylene and propylene.
14. The method for producing ethylene, propylene and aromatic hydrocarbon according to claim 1 or 2, wherein the steam cracking in the step (4) is operated at a reaction temperature of 780 ℃ to 850 ℃ and a residence time of 0.01 to 3 seconds.
15. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1 or 2, wherein the dry gas separation in step (4) is carried out using the same gas separation apparatus comprising a rectifying column and auxiliary equipment.
16. A reaction system for producing ethylene, propylene and aromatic hydrocarbons, comprising a reaction device, a catalyst and a reactant stream; the reaction device comprises a catalytic cracking reactor, a regenerator, a first oil-gas separation system, a second oil-gas separation system, an aromatization reactor and an alkane dehydrogenation reactor which are communicated in sequence; the regeneration agent outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and gas-solid separation equipment, the spent agent outlet of the gas-solid separation equipment is communicated with the regenerator, the oil-gas outlet of the gas-solid separation equipment is communicated with the first oil-gas separation system, the C4 outlet of the first oil-gas separation system is communicated with the aromatization reactor, the outlet of the aromatization reactor is communicated with a second oil-gas separation system, the C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and the product outlet of the dehydrogenation reactor is communicated with the catalytic cracking reactor; the catalytic cracking catalyst circularly flows in the catalytic cracking reactor and the regenerator, the aromatization catalyst is filled in the aromatization reactor, and light hydrocarbon raw materials are introduced through a raw material inlet of the catalytic cracking reactor and react in the reaction device.
17. The reaction system for producing ethylene, propylene and aromatic hydrocarbons according to claim 16, wherein said reaction apparatus further comprises a gas separation apparatus and a steam cracker; the dry gas outlet and the liquefied gas outlet of the first and second oil-gas separation systems are communicated with the gas separation device, and the ethane and propane outlets of the gas separation device are communicated with the steam cracking furnace.
18. The reaction system for producing ethylene, propylene and aromatic hydrocarbons according to claim 16 or 17, wherein the catalytic cracking reactor is a riser reactor, the aromatization reactor is a fixed bed reactor, and the alkane dehydrogenation reactor is a fixed bed reactor.
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