CN112723970B - Method for producing propylene, ethylene and aromatic hydrocarbon from heavy oil and catalytic conversion device - Google Patents
Method for producing propylene, ethylene and aromatic hydrocarbon from heavy oil and catalytic conversion device Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 69
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 51
- -1 propylene, ethylene Chemical group 0.000 title claims abstract description 50
- 239000000295 fuel oil Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 29
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 86
- 235000019198 oils Nutrition 0.000 claims description 86
- 238000000926 separation method Methods 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 42
- 239000003502 gasoline Substances 0.000 claims description 35
- 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 25
- 239000002808 molecular sieve Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 20
- 239000002283 diesel fuel Substances 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000571 coke Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000003027 oil sand Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000005977 Ethylene Substances 0.000 abstract description 11
- 238000009825 accumulation Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000306 component Substances 0.000 description 41
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000001993 wax Substances 0.000 description 11
- 230000000087 stabilizing effect Effects 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- 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
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/80—Mixtures of different zeolites
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing propylene, ethylene and aromatic hydrocarbon by heavy oil and a catalytic conversion device, comprising the following steps: carrying out catalytic cracking reaction on a heavy oil raw material in a first reactor, and separating out at least ethylene, propylene, an aromatic hydrocarbon product and a first carbon four component from reaction oil gas; the first carbon four-component is subjected to catalytic cracking reaction in a second reactor, and ethylene and propylene products and a second carbon four-component are at least separated from reaction oil gas; the second carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and at least ethylene, propylene and aromatic hydrocarbon products are separated from reaction products. The method for producing propylene, ethylene and aromatic hydrocarbon by using heavy oil and the catalytic conversion device solve the problem of alkane accumulation in the carbon four-cycle, greatly increase the yield of ethylene, propylene and aromatic hydrocarbon, and greatly reduce the energy consumption and the operation cost of the carbon four-cycle.
Description
Technical Field
The invention relates to a method and a device for producing chemical raw materials from petroleum raw materials, in particular to a method and a device for producing ethylene, propylene and aromatic hydrocarbon from heavy oil.
Technical Field
Ethylene, propylene and BTX aromatics are growing in demand each year as a large group of basic chemical feedstocks. The catalytic cracking is used as a device for processing heavy oil to produce gasoline, and a large amount of propylene is also byproduct, and is a main supplement source of the propylene market. Wherein, the deep catalytic cracking (such as DCC process) using more selective molecular sieve (ZSM-5) as an active center can produce propylene in large quantity and produce certain propylene and BTX aromatic hydrocarbon as byproducts. 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 added as a raw material.
The technology for preparing propylene from liquefied gas rich in olefin takes liquefied gas with lower added value as raw material, and the carbon tetraolefin in the liquefied gas is cracked under the action of catalyst to generate propylene and ethylene with high added value and aromatic hydrocarbon-rich gasoline component with high octane value, for example, in the DCC family technology, C4 olefin is returned to a catalytic cracking device to be cracked again to generate ethylene and propylene. Meanwhile, in 2020, ethanol gasoline is popularized nationwide, so that 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 reprocessing and utilization of C4 olefins are concerned.
CN1034586A discloses a method for producing low-carbon olefins by catalytic cracking, which adopts gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and a mixture as raw materials, and adopts a Y-type molecular sieve and a phosphorus-containing ZSM-5 molecular sieve as active centers; a fluidized bed or a riser reactor is adopted; the operation conditions are that the pressure is 120 kPa-400 kPa, the reaction temperature is 480-680 ℃, the retention time is 0.1-6 seconds, the agent-oil ratio is 4-20, and the atomized water vapor accounts for 1-50 percent of the weight of the raw materials. This method, despite modifying the catalyst, has similar problems to CN104878, i.e. high reaction temperature, more methane by-product, and generation of large amount of unusable carbon four and diesel.
CN1056595A discloses a method for low-producing carbon olefin by using multi-stage feeding. The method adopts ethane to residual oil as raw materials, and uses an alkaline earth metal-containing molecular sieve as an active center; a riser reactor is adopted; the operation conditions are that the pressure is 130 kPa-400 kPa, the reaction temperature is 600-900 ℃, the residence time is 0.1-6 seconds and the catalyst-oil ratio is 5-100, and the multi-stage feeding and cracking are carried out from high to low according to different cracking difficulties. Although the method solves the problem of byproducts such as carbon four, the method also has the problem of more byproducts such as methane and coke for raw materials with poor processing property,
CN1065963A discloses a method for producing low-carbon olefins by multi-stage feeding, which takes gasoline, vacuum wax oil and residual oil as raw materials, and takes a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; adopting a riser reactor and a fluidized bed reactor; the operating conditions are that the pressure is 130 kPa-400 kPa, the reaction temperature is 500-600 ℃, the riser residence time is 1-5 seconds, and the space velocity of the fluidized bed is 0.2-20hr -1 And the agent-oil ratio is 6-15, the atomized water vapor accounts for 1-60% of the weight of the raw material, wherein the mixture of the vacuum wax oil and the residual oil enters the bottom of the riser reactor, the gasoline component enters the fluidized bed reactor, and the riser reactor and the fluidized bed reactor are connected in series. The method can not solve the problem that the by-products of methane, carbon four and diesel oil are more.
CN102337148A discloses a method for producing low-carbon olefin by using gasoline rich in four to eight carbons as raw material. The method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; adopting a riser reactor and a fluidized bed reactor; the operating conditions include 150-300 kPa of pressure, 480-680 deg.c of reaction temperature, riser residence time of 1-5 sec and fluidized bed airspeed of 0.2-30hr -1 And the agent-oil ratio is 8-40. The method cannot solve the accumulation of alkane components despite the recycling of four to eight carbon olefins.
CN101362961A discloses a method for producing low-carbon olefin and aromatic hydrocarbon by using hydrocarbons with the temperature of 160-270 ℃ as raw materials, and the method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the operating conditions are that the pressure is 100 kPa-1000 kPa, the reaction temperature is 450-750 ℃, and the space velocity is 1-150hr -1 And the agent-oil ratio is 1-150. The method solves the problem of the export of part of diesel oil.
CN101747928A discloses a method for producing low-carbon olefins and aromatics by using vacuum wax oil and residual oil as raw materials. The method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the feed reactor and the C4 olefin-250 ℃ product recycle reactor share a single regenerator. The method solves the problem of part of diesel oil, but cannot solve the problem of accumulation of alkane components and polycyclic aromatic hydrocarbon components.
CN 1667089A discloses a method for producing low-carbon olefins, which uses gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials, first hydrotreats the raw materials and recycle streams, and then enters a catalytic cracking reactor. Wherein the gas recycle is ethane, propane and C4. The liquid circulation feed is C5-C6, heavy gasoline aromatic raffinate oil, LCO, HCO and slurry oil. Although the method solves the problem of the outlet of most byproducts, the method cannot solve the problem of the accumulation of alkane components and polycyclic aromatic hydrocarbon components.
CN101747928A discloses a method for producing low-carbon olefins and aromatics, which uses vacuum wax oil and residual oil as raw materials and combines catalytic cracking and steam cracking. The method comprises the steps of separating the product of catalytic cracking, feeding the alkane from c2 to gasoline into a steam cracking reactor, and returning the butene, the recycle oil and the oil slurry into the catalytic cracking reactor. Aromatic hydrocarbons are produced by an aromatic extraction process. The method solves the problem of accumulation of alkane components and polycyclic aromatic hydrocarbon components. But the separation of the olefin and the alkane with the components above C4 is high in energy consumption and cannot be paid.
The reaction speed of the tetracarbon is obviously slower than that of the tetracarbon, so that the conversion rate of the tetracarbon is higher and the conversion rate of the tetracarbon is extremely low in the mixed tetracarbon reaction process in the riser reactor. In the prior art, in the carbon four-component cycle reaction process, unreacted carbon tetralkyl hydrocarbon is retained in the carbon four-component, and alkane generated by raw oil is continuously accumulated in a cycle material flow. There is caused a problem that if the carbon four cycle ratio is not increased, the propylene yield is lowered due to the decrease in the olefin content in carbon four. If the carbon four cycle ratio is increased, the energy consumption is greatly increased.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of alkane component accumulation in the process of preparing low-carbon olefins from hydrocarbon oil in the prior art, and provide a method for producing ethylene, propylene and aromatic hydrocarbon from heavy oil, which reduces the accumulation of alkane components and has high product yield.
The second technical problem to be solved by the invention is to provide a catalytic conversion device for producing ethylene, propylene and aromatic hydrocarbon from heavy oil.
The invention provides a method for producing propylene, ethylene and aromatic hydrocarbon by using heavy oil, which comprises the following steps:
(1) The heavy oil raw material enters a first reactor, and is in contact reaction with a first strand of catalyst from a regenerator, the mixture of oil gas and catalyst obtained by the reaction is subjected to gas-solid separation, and the separated catalyst to be regenerated is sent to the regenerator to be coked and regenerated and heated; the separated reaction oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a first separation system, and ethylene, propylene, aromatic hydrocarbon and a first carbon four component are further separated;
(2) Introducing the first carbon four component alone or together with an external carbon four component into a second reactor, contacting and reacting with a second strand of regenerated catalyst from a regenerator, carrying out gas-solid separation on an oil gas and catalyst mixture obtained by the reaction, and feeding the separated spent catalyst into the regenerator to burn coke for regeneration and raise the temperature; the separated oil gas is separated into dry gas, liquefied gas, gasoline and diesel oil through a second separation system, and ethylene, propylene and a second carbon component are further separated;
(3) The second carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a third separation system, so that ethylene, propylene and aromatic hydrocarbon products are further separated.
The invention provides a catalytic conversion device for producing propylene, ethylene and aromatic hydrocarbon by using heavy oil, which is used for the method for producing propylene, ethylene and aromatic hydrocarbon by using heavy oil, and comprises the following steps: (1) The first reactor, the gas-solid separation equipment and the first separation system are communicated in sequence; (2) The second reactor, the gas-solid separation equipment and the second oil-gas separation system are communicated in sequence; (3) An aromatization reactor and a third separation system which are communicated in sequence; (4) The regenerator is provided with a regenerated catalyst inclined pipe which is communicated with the bottoms of the first reactor and the second reactor respectively, and a spent catalyst inclined pipe of the regenerator is communicated with a solid particle outlet of the gas-solid separation equipment; wherein, the C4 outlet of the first separation system is communicated with the raw material inlet of the second reactor, and the C4 outlet of the second oil-gas separation system is communicated with the aromatization reactor.
The method for producing propylene, ethylene and aromatic hydrocarbon by using heavy oil and the catalytic conversion device have the beneficial effects that:
the method provided by the invention takes the heavy oil as the raw material to produce the propylene, the ethylene and the aromatic hydrocarbon, and can produce the ethylene, the propylene and the aromatic hydrocarbon to the maximum extent. The method solves the problem of alkane accumulation in the carbon four-cycle, not only greatly increases the yields of ethylene, propylene and aromatic hydrocarbon, but also greatly reduces the energy consumption and the operation cost of the carbon four-cycle; the method reduces the coke yield of the catalytic cracking unit required to meet the heat balance; the heat extraction load of the aromatization device can be reduced, and the energy consumption of the aromatization device is reduced.
Drawings
FIG. 1 is a schematic flow diagram of a process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to the present invention.
FIG. 2 is a schematic flow diagram of the oil-gas separation process of the method for producing propylene, ethylene and aromatic hydrocarbons from heavy oil provided by the invention.
FIG. 3 is a schematic flow chart of a process for producing ethylene and propylene from the heavy oil in comparative examples 1 and 2.
Wherein: 202-a first reactor; 203. 224-a settler; 303. 222-a stripper; 206-a regenerator; 211-a first separation system; 226-a second separation system; 230-an aromatization reactor; 232-third separation system, others are pipelines.
Detailed Description
The following specifically describes embodiments of the present invention:
a process for producing propylene, ethylene and aromatics from heavy oil, comprising:
(1) The heavy oil raw material enters a first reactor, contacts and reacts with a first strand of catalyst from a regenerator, the mixture of oil gas and catalyst obtained by the reaction is subjected to gas-solid separation, and the separated catalyst to be generated is sent to the regenerator for coke burning regeneration and temperature rise; the separated reaction oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a first separation system, and further ethylene, propylene, aromatic hydrocarbon and a first carbon four component are separated;
(2) Introducing the first carbon four component into a second reactor independently or together with an external carbon four component, carrying out contact reaction with a second strand of regenerated catalyst from a regenerator, carrying out gas-solid separation on an oil gas and catalyst mixture obtained by the reaction, and feeding the separated spent catalyst into the regenerator to burn coke for regeneration and raise the temperature; the separated oil gas is separated into dry gas, liquefied gas, gasoline and diesel oil through a second separation system, and ethylene, propylene and a second carbon component are further separated;
(3) The second four carbon components enter an aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a third separation system, so that ethylene, propylene and aromatic hydrocarbon products are further separated.
In the method provided by the invention, the catalytic cracking raw material is one or a mixture of more of wax oil, atmospheric residue oil, vacuum residue oil, coking wax oil, deasphalted oil, furfural refined raffinate oil, coal liquefaction oil, oil sand oil, shale oil, distillate oil obtained by F-T synthesis and animal and vegetable oil. Other organic compounds or hydrocarbons with carbon number greater than 16 are also possible.
The catalyst is a catalytic cracking catalyst and contains an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein the MFI structure molecular sieve accounts for 105-60 wt%, preferably 3010-50 wt%, the Y-type molecular sieve accounts for 1-40 wt%, preferably 1-230 wt%, the clay accounts for 10-70 wt%, preferably 15-45 wt%, and the binder accounts for 105-40 wt%, preferably 205-35 wt%, based on the total weight of the catalyst.
The first reactor is a reactor combined by one or more than one of a riser reactor, a turbulent flow bed reactor and a fast bed reactor. The operating conditions of the first reactor were: 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 。
The catalyst and the oil gas in the first reactor are separated by a cyclone gas-solid separator, a settler and the like which are well known in the art.
The regenerator is a regenerator of various forms in the art that uses air or air mixed oxygen-rich gas to react with coke on the spent catalyst, burns off the coke on the spent catalyst to restore the activity of the spent catalyst (called regenerated catalyst), and raises the catalyst temperature to 600 ℃ to 760 ℃ to bring heat and catalytic media back to the reactor for the reaction.
The first separation system can adopt one or more of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower.
The second reactor is a reactor combined by one or more than one of a riser reactor, a turbulent flow bed reactor and a fast bed reactor. The operating conditions of the second 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 。
The catalyst and oil gas separation in the second reactor adopts cyclone gas-solid separator, settler, etc. and the separated catalyst with adsorbed oil gas is stripped in a stripper.
The first C4 four-component contains C4 olefin and C4 alkane, and the olefin content is more than 20wt%; the second C4 olefin and C4 alkane are contained in the second C four component, and the olefin content is more than 40wt%; preferably, the olefin content of the extrinsic carbon four component is greater than 20wt%.
In the method for producing light olefins from heavy hydrocarbon oil, the first reactor and the second reactor are separately provided with a settler and a stripper, and are separately provided with a separation system.
The second separation system can adopt one or a plurality of combinations of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower.
In the aromatization reactor, the second four-carbon component is subjected to aromatization reaction in the aromatization reactor to generate dry gas, liquefied gas and a gasoline fraction rich in aromatic hydrocarbon, wherein the aromatic hydrocarbon is C6 to C10 monocyclic aromatic hydrocarbon.
SaidThe operating conditions of the aromatization reactor were: 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 。
The aromatization reactor adopts an aromatization catalyst and 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, VIB, VIII, IIB and VIIB elements, and the heat-resistant inorganic oxide is preferably silicon oxide and aluminum oxide.
The third separation system can adopt one or a plurality of combinations of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower.
The method is described below with reference to the accompanying drawings, but the invention is not limited thereto.
FIG. 1 is a schematic flow diagram of a process for producing propylene, ethylene and aromatics from heavy oil. As shown in FIG. 1, a heavy oil feedstock is preheated and then enters a first reactor 202 via line 201 to contact and react with a thermally regenerated catalytic catalyst from a regenerator 206 via line 209, the first reactor being a riser reactor. The mixture of the reaction oil gas and the catalyst enters a settler 203, a gas-solid separation device is arranged in the settler 203, the oil gas and the catalyst are separated in the settler 203, and the separated catalyst with carbon enters a regenerator 206 through a steam stripping section 303 and enters a line 205 for coke burning and regeneration. The air via line 301 in the regenerator 206 burns the coke from the catalyst to restore activity, and then enters the bottom of the first reactor 202 via line 209 to participate in the reaction.
The separated oil gas enters a first separation system through a pipeline 204, and is separated by the first separation system to obtain dry gas 302, propylene 219, propane 220, product gasoline 216, product diesel 212 and slurry oil 213. The first separation system comprises a fractionating tower, a post-absorption stabilizing system and a gas separation device.
The first carbon four component 221 enters the second reactor 210 to contact with the regenerated catalyst heated by the regenerator 206 through the pipeline 200, the generated oil gas and catalyst enter the settler 224, a gas-solid separation device is arranged in the settler 224, the oil gas and the catalyst are separated in the settler 224, the separated catalyst with carbon enters the regenerator 206 through the steam stripping section 222 through the pipeline 223 to be burnt and regenerated for recovering activity, and then enters the bottom of the reactor 210 through the pipeline 200 to circularly participate in the reaction.
The separated oil gas enters a second separation system through a pipeline 225, and dry gas 231, propylene 234, propane 235, a second carbon four component 236, gasoline 304 and diesel oil 227 are separated out, wherein the first separation system comprises a fractionating tower, a post-absorption stabilizing system and a gas separation device.
The second carbon four component 236 enters the aromatization reactor 237 and contacts with an aromatization catalyst to carry out aromatization reaction. The products are separated to obtain gasoline 239 rich in aromatic hydrocarbon, dry gas 305 and liquefied gas 238.
FIG. 2 is a schematic flow diagram of the oil-gas separation process of the method for producing propylene, ethylene and aromatic hydrocarbons from heavy oil provided by the invention. As shown in fig. 2, the oil gas separated from the settler of the first reactor enters a fractionating tower 211 of the first separation system through a pipeline 204, a product diesel oil 212 is extracted from the middle part of the fractionating tower 211, a product slurry oil 213 is extracted from the bottom part, products below the gasoline obtained from the top of the fractionating tower 211 enter a rear absorption stabilizing system 215 of the first separation system through a pipeline 214, a product gasoline 216, a dry gas 302 and a liquefied gas 217 separated from the stabilizing system enter a gas separation device 218, and propylene 219, propane 220 and a first carbon four component 221 are separated from the liquefied gas 217.
Oil gas separated by a settler of the second reactor enters a fractionating tower 226 of a second separation system through a pipeline 225, product diesel oil 227 is extracted from the bottom of the fractionating tower 226, products below the gasoline obtained from the top of the fractionating tower 226 enter a post-absorption stabilizing system 230 of the second separation system through a pipeline 229, product gasoline 304, dry gas 231 and liquefied gas 232 separated by the stabilizing system 230, and liquefied gas 232 enters a gas separation device 233 to separate propylene 234, propane 235 and a second carbon four-component 236.
The effects of the process for producing ethylene, propylene and aromatic hydrocarbons from heavy oil provided by the present invention are illustrated below by examples and comparative examples, but the present invention is not limited thereto.
In the comparative example and the example, the heavy oil raw material A used is hydrogenated residual oil which is taken from the Shijiazhuan oil refinery of the China petrochemical Co Ltd; the heavy oil raw material B is straight-run wax oil and is obtained from Yanshan division of the China petrochemical industry, inc. The properties of the heavy oil feedstocks a, B are shown in table 1. The catalyst used is DMMC-1 catalyst produced by catalyst division of China petrochemical company Limited. The properties are shown in Table 2.
Comparative examples 1 to 2
Comparative examples 1-2 a schematic flow diagram of a process for producing ethylene and propylene by catalytic cracking of heavy oil as shown in fig. 2 is shown in fig. 2: heavy oil raw materials enter a main reactor 102 of a catalytic cracking riser after being preheated through a pipeline 101 to contact with regenerated catalytic catalysts coming from a regenerator 106 through a pipeline 109, generated oil gas and catalysts enter a settler 103, the oil gas and the catalysts are separated in the settler 103, and the separated catalysts with carbon enter the regenerator 106 through a pipeline 105 after being stripped by a stripper 402 and are burnt. Air via line 108 in regenerator 106 burns coke from the catalyst to restore activity and then enters the bottom of reactor 102 via line 109 to recycle to participate in the reaction.
The separated oil gas enters a fractionating tower 111 through a pipeline 104, the product diesel oil 112 is extracted from the middle part of the fractionating tower 111, and the product slurry oil 113 is extracted from the bottom part. The products below the gasoline obtained from the top of the fractionating tower 111 enter a post-absorption stabilizing system 115 through a pipeline 114, dry gas 401, liquefied gas 117 and gasoline 116 separated by the stabilizing system are stabilized, and the liquefied gas 117 enters a gas separation device 118 to separate propylene 119, propane 120 and carbon four components 121.
The carbon four components 121 enter a catalytic cracking riser secondary reactor 110 to contact with a regenerated catalyst heated by a regenerator 106 through a pipeline 100, the generated oil gas and the catalyst enter a settler 103, and the catalytic cracking riser secondary reactor 110 and the catalytic cracking riser main reactor 102 share the same settler and regenerator.
The respective reaction operating conditions of comparative examples 1-2 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) heavy oil raw materials enter a first reactor to contact and react with a first strand of catalyst from a regenerator, a mixture of oil gas and the catalyst obtained by the reaction is subjected to gas-solid separation, and the separated spent catalyst is sent to the regenerator to be burnt and regenerated and heated; the separated reaction oil gas is separated into dry gas, propylene, propane, a first carbon four component, gasoline, diesel oil and oil slurry through a first separation system;
(2) The first carbon four component is separately contacted with a second strand of regenerated catalyst from a regenerator for reaction, the mixture of oil gas and catalyst obtained by the reaction is subjected to gas-solid separation, and the separated catalyst to be regenerated is sent to the regenerator for coke burning regeneration and temperature rise; the separated oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a second separation system, and further ethylene and propylene products and a second carbon four component are separated;
(3) The second carbon four component enters a carbon four aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a third separation system, so that ethylene, propylene and aromatic hydrocarbon products are further separated.
The reaction conditions of examples 1-2 are shown in Table 3, and the product yields are shown in Table 4.
As can be seen from the results in table 4, with heavy oil feedstock a, the process of the present invention example 1 provides a 0.11 reduction in carbon four feed/feedstock, a 0.63 percentage point increase in ethylene yield, a 1.38 percentage point increase in propylene yield, and a 1.67 percentage point increase in aromatics (BTX) yield, as compared to comparative example 1. With heavy oil feedstock B, the process of the present invention example 2 reduced the carbon four feed/feedstock by 0.21, increased the ethylene yield by 1.20 percentage points, increased the propylene yield by 1.72 percentage points, and increased the aromatics (BTX) yield by 3.84 percentage points, as compared to comparative example 2.
TABLE 1
TABLE 2
TABLE 3 operating conditions of the reactors
| Item | Comparative example 1 | Example 1 | Comparative example 2 | Example 2 |
| Raw oil | Starting materials A | Starting materials A | Raw material B | Raw material B |
| First reactor | ||||
| Catalyst and process for preparing same | DMCC-1 | DMCC-1 | DMCC-1 | DMCC-1 |
| Reaction pressure/MPa | 0.2 | 0.2 | 0.28 | 0.28 |
| Reaction temperature/. Degree.C | 555 | 555 | 620 | 620 |
| Regenerator temperature/. Degree.C | 690 | 690 | 710 | 710 |
| Ratio of agent to oil | 10 | 10 | 15 | 15 |
| Reaction space velocity/h -1 | 14 | 14 | 5 | 5 |
| Atomized steam/%) | 25 | 25 | 15 | 15 |
| Second reactor | ||||
| Carbon four feed/stock oil | 0.25 | 0.14 | 0.40 | 0.19 |
| Reaction pressure MPa | 0.2 | 0.2 | 0.28 | 0.28 |
| Reaction temperature/. Degree.C | 600 | 600 | 640 | 640 |
| Regenerator temperature/. Degree.C | 690 | 690 | 710 | 710 |
| Ratio of agent to oil | 8 | 8 | 12 | 12 |
| Reaction space velocity/h -1 | 50 | 50 | 8 | 8 |
| Atomized steam/%) | 10 | 10 | 25 | 25 |
| Aromatization reactor conditions: | ||||
| reaction temperature/. Degree.C | 450 | 460 | ||
| Reaction pressure/MPa | 1 | 1.2 | ||
| Reaction space velocity/h -1 | 1 | 1.2 |
TABLE 4 product yields
| Comparative example 1 | Example 1 | Comparative example 2 | Example 2 | |
| Product yield, wt.% | ||||
| H2-C2 | 13.69 | 14.52 | 16.11 | 17.35 |
| C3-C4 | 22.93 | 21.31 | 39.25 | 36.86 |
| C5+ gasoline | 29.44 | 30.18 | 26.89 | 27.85 |
| Diesel oil | 16.30 | 16.32 | 8.68 | 8.72 |
| Heavy oil | 5.70 | 5.71 | 2.18 | 2.21 |
| Coke | 11.94 | 11.96 | 6.89 | 7.01 |
| Ethylene | 8.00 | 8.63 | 10.67 | 11.87 |
| Propylene (PA) | 19.05 | 20.43 | 30.26 | 31.98 |
| BTX | 9.35 | 11.02 | 7.50 | 11.34 |
Claims (13)
1. A process for producing propylene, ethylene and aromatics from heavy oil comprising:
(1) The heavy oil raw material enters a first reactor, contacts and reacts with a first strand of regenerated catalyst from a regenerator, the mixture of oil gas and catalyst obtained by the reaction is subjected to gas-solid separation, and the separated catalyst to be regenerated is sent to the regenerator to be coked and regenerated and heated; the separated reaction oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a first separation system, and further ethylene, propylene, aromatic hydrocarbon and a first carbon four component are separated;
(2) Introducing the first carbon four component alone or together with external carbon four components into a second reactor, contacting and reacting with a second strand of regenerated catalyst from a regenerator, carrying out gas-solid separation on an oil gas and catalyst mixture obtained by the reaction, and delivering the separated spent catalyst to the regenerator to burn coke for regeneration and raise the temperature; the separated oil gas is separated into dry gas, liquefied gas, gasoline and diesel oil through a second separation system, and ethylene, propylene and a second carbon component are further separated;
(3) The second four carbon components enter an aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a third separation system, so that ethylene, propylene and aromatic hydrocarbon products are further separated.
2. The process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 1, wherein the heavy oil feedstock is selected from one or more of wax oil, atmospheric residue, vacuum residue, coker wax oil, deasphalted oil, furfural refined raffinate oil, coal liquefaction oil, oil sand oil, shale oil, distillate oil obtained by F-T synthesis, and animal and vegetable oils.
3. The process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 1, wherein the catalyst in step (1) (2) is a catalytic cracking catalyst comprising an MFI-structured molecular sieve, a Y-type molecular sieve, clay and a binder, and wherein the MFI-structured molecular sieve is contained in an amount of 5 to 60 wt%, the Y-type molecular sieve is contained in an amount of 1 to 40wt%, the clay is contained in an amount of 10 to 70 wt% and the binder is contained in an amount of 5 to 40wt%, based on the total weight of the catalyst.
4. The process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 3, wherein the MFI structure molecular sieve content is 10 to 50 wt%, the Y-type molecular sieve content is 1 to 30 wt%, the clay content is 15 to 45 wt% and the binder content is 5 to 35 wt%, based on the total weight of the catalyst.
5. The process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 1, wherein the first reactor is one or a combination of riser reactor, turbulent bed reactor and fast bed reactor; the operating conditions of the first reactor were: 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 。
6. The method for producing propylene, ethylene and aromatic hydrocarbons with heavy oil according to claim 1, wherein the second reactor is one or more of a riser reactor, a turbulent bed reactor and a fast bed reactor; operation of the reactorThe conditions are as follows: 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 process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 1, wherein said first C4-tetrad comprises C4 olefins and C4 alkanes, and has an olefin content of greater than 20wt%; the second C4 olefin and C4 alkane are contained in the second C four component, and the olefin content is more than 40wt%; the olefin content of the extrinsic carbon four component is greater than 20wt%.
8. The process for producing propylene, ethylene and aromatic hydrocarbons with heavy oil according to claim 1, wherein the aromatization reactor is operated under the following conditions: 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 。
9. The method for producing propylene, ethylene and aromatic hydrocarbons by using heavy oil according to claim 1, wherein the aromatization catalyst comprises a molecular sieve, a metal active component and a heat-resistant inorganic oxide carrier, and the metal active component is one or more selected from rare earth elements, VIB, VIII, IIB and VIIB elements.
10. The process for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 9, wherein the refractory inorganic oxide is silica or alumina.
11. A catalytic conversion unit for producing propylene, ethylene and aromatic hydrocarbons from heavy oil, which is used in the method for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to any one of claims 1 to 10, and comprises: (1) The first reactor, the gas-solid separation equipment and the first separation system are communicated in sequence; (2) The second reactor, the gas-solid separation equipment and the second oil-gas separation system are communicated in sequence; (3) An aromatization reactor and a third separation system which are communicated in sequence; (4) The regenerator has a regenerated catalyst inclined pipe communicated with the bottoms of the first reactor and the second reactor, and a spent catalyst inclined pipe communicated with the solid particle outlet of the gas-solid separation equipment; wherein, the C4 outlet of the first separation system is communicated with the raw material inlet of the second reactor, and the C4 outlet of the second oil-gas separation system is communicated with the aromatization reactor.
12. The catalytic conversion apparatus for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 11, wherein the first and second reactors are riser reactors combined by one or more of a riser reactor, a turbulent bed reactor and a fast bed reactor, and the aromatization reactor is a fixed bed reactor.
13. The catalytic converter for producing propylene, ethylene and aromatic hydrocarbons from heavy oil according to claim 11 or 12, wherein the first separation system, the second oil-gas separation system, and the third separation system are one or more of a fractionating tower, a rectifying tower, an absorption tower, and a desorption tower.
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