CN117384665A - Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking - Google Patents
Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking Download PDFInfo
- Publication number
- CN117384665A CN117384665A CN202210794829.8A CN202210794829A CN117384665A CN 117384665 A CN117384665 A CN 117384665A CN 202210794829 A CN202210794829 A CN 202210794829A CN 117384665 A CN117384665 A CN 117384665A
- Authority
- CN
- China
- Prior art keywords
- catalytic cracking
- gas
- catalyst
- cyclone
- inlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 41
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- 238000005243 fluidization Methods 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 44
- 239000002808 molecular sieve Substances 0.000 claims description 21
- 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 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 229940092782 bentonite Drugs 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for producing light olefins and aromatic hydrocarbons by catalytic cracking, which comprises the following steps: enabling a first fluidizing medium, a catalyst and raw oil to enter the top end of a downer reactor and to perform first fluidization to obtain a first fluidizing material moving downwards; and introducing a second fluidizing medium tangentially into the downer reactor through a cyclone air inlet to drive the first fluidizing material to perform catalytic cracking reaction under the state of cyclone flow and downward flow, then performing gas-solid separation and steam stripping to obtain a spent catalyst and reaction product oil gas, and regenerating the spent catalyst and returning the spent catalyst to perform the catalytic cracking reaction. The invention also provides a system for producing the low-carbon olefin and the aromatic hydrocarbon by catalytic cracking. Through the technical scheme, the invention strengthens the gas-solid contact between the raw oil and the catalyst, thereby effectively improving the conversion rate and selectivity of the catalytic cracking production of low-carbon olefin and aromatic hydrocarbon.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking and a system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking.
Background
Catalytic cracking diesel (LCO) is rich in aromatic hydrocarbon and is a potential ideal raw material for producing aromatic hydrocarbon. The monocyclic aromatic hydrocarbon has the cracking property, can be directly catalytically cracked to produce aromatic hydrocarbon, and is easy to saturate into monocyclic aromatic hydrocarbon after the polycyclic aromatic hydrocarbon is hydrotreated. Therefore, by hydrotreating LCO and combining with a catalytic cracking process, it is expected to increase the aromatic productivity.
US6656346B2 discloses a catalytic cracking process employing a downer reactor for carrying out catalytic cracking reactions at high severity to produce propylene.
However, the conversion and selectivity of the existing catalytic cracking process still need to be further improved.
Disclosure of Invention
The invention aims to further improve the conversion rate and selectivity of low-carbon olefin and aromatic hydrocarbon produced by catalytic cracking.
In order to achieve the above object, the present invention provides a method for producing light olefins and aromatics by catalytic cracking, comprising: allowing a reaction material containing a first fluidizing medium, a catalyst and a raw oil to enter the top end of a downer reactor and to perform first fluidization to obtain a first fluidizing material moving downwards; and introducing a second fluidizing medium tangentially into the downer reactor through a cyclone air inlet to drive the first fluidizing material to perform catalytic cracking reaction under the state of cyclone flow and downward flow, then performing gas-solid separation and steam stripping to obtain a spent catalyst and reaction product oil gas, and regenerating the spent catalyst and returning the spent catalyst to perform the catalytic cracking reaction.
The invention also provides a system for producing light olefins and aromatic hydrocarbons by catalytic cracking, which is characterized by comprising a downstream bed reactor, a gas-solid rapid separation device, a stripper and a regenerator which are connected in sequence, wherein a discharge port of the regenerator is connected with a catalyst inlet of the fluidized bed reactor; wherein, the side wall of the inlet of the downer reactor is tangentially provided with a rotational flow air inlet.
Through the technical scheme, the gas-solid contact of the raw oil and the catalyst is enhanced through rotational flow, so that the conversion rate and selectivity of producing low-carbon olefin and aromatic hydrocarbon through catalytic cracking are effectively improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
fig. 1 is a schematic diagram of a system structure in a preferred embodiment of the present invention.
Fig. 2 is a schematic view of a swirl inlet according to a preferred embodiment of the present invention.
Fig. 3 is a top view of the swirl intake of fig. 2.
Description of the reference numerals
In fig. 1, 1 is a first fluidizing medium; 2 is an inlet distributor; 3 is a spool valve to be created; 4 is an oil inlet nozzle; 5 is a second fluidizing medium; 6 is a rotational flow air inlet; 7 is a downer reactor; 8 is a product oil gas discharge pipeline; 9 is a cyclone separator; 10 is a gas-solid rapid separator; 11 is a stripped oil gas pipeline; 12 is a catalyst line; 13 is stripping steam; 14 is a stripper; 15 is a regenerative slide valve; 16 is a regeneration medium; 17 is a riser regenerator; 18 is a riser outlet cyclone; 19 is a settler; a 20-settler cyclone; 21 is a flue gas outlet line.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a method for producing light olefins and aromatic hydrocarbons by catalytic cracking, which comprises the following steps: allowing a reaction material containing a first fluidizing medium, a catalyst and a raw oil to enter the top end of a downer reactor and to perform first fluidization to obtain a first fluidizing material moving downwards; and introducing a second fluidizing medium tangentially into the downer reactor through a cyclone air inlet to drive the first fluidizing material to perform catalytic cracking reaction under the state of cyclone flow and downward flow, then performing gas-solid separation and steam stripping to obtain a spent catalyst and reaction product oil gas, and regenerating the spent catalyst and returning the spent catalyst to perform the catalytic cracking reaction.
The inventor of the present invention found that the rigorous reaction conditions and the high gas-solid contact efficiency are favorable for improving the conversion rate and selectivity of producing low-carbon olefin and aromatic hydrocarbon through catalytic cracking reaction. However, the existing downer reactor has low gas-solid contact efficiency due to low concentration of bed particles and weak back mixing degree, thereby affecting the conversion rate and selectivity of the catalytic cracking reaction. The inventors of the present invention have further found that if the catalytic cracking reaction is carried out in a downer reactor in a swirling state, the gas-solid contact efficiency can be effectively enhanced, so that more severe reaction conditions (higher temperature and larger catalyst-to-oil ratio) can be used and the gas-solid residence time can be prolonged, the reaction conversion and selectivity can be improved, and the yields of olefin and aromatic hydrocarbon products can be increased.
Wherein, 2-6 cyclone inlets can be arranged on one downer reactor, preferably 1-3 groups of cyclone inlets are arranged, and each group of cyclone inlets comprises 2 cyclone inlets which are symmetrically arranged; the swirl inlet is lower than the inlet of the raw oil.
Wherein, optionally, the weight flow ratio of the first fluidizing medium to the second fluidizing medium is 0.01-1:1.
wherein the gas linear velocity of the swirling flow may be typically 0.1 to 10m/s, preferably 1 to 5m/s, and the gas angular velocity of the swirling flow may be 0.01 to 10s -1 Preferably 0.1 to 5s -1 . Wherein, can pass throughAnd adjusting the rotational gas angular velocity such as the weight flow rate ratio, the linear velocity ratio and the like of the first fluidizing medium and the second fluidizing medium.
Optionally, wherein the aspect ratio of the downer reactor is from 2 to 50:1, preferably 5-20:1.
optionally, the conditions of catalytic cracking include: the reaction temperature is 500-800 ℃, preferably 560-690 ℃; the reaction pressure is 0.1-2.0MPa, preferably 0.3-1MPa; the weight ratio of the agent to the oil is 10-150, preferably 15-50; the residence time is from 0.2 to 10 seconds, preferably from 0.5 to 5 seconds.
Alternatively, the conditions for catalyst regeneration may include: the regeneration temperature is 550-850 ℃, and the regeneration medium is air.
Optionally, the fluidizing medium is at least one of steam and dry gas.
Optionally, the catalyst comprises 10-60wt% of molecular sieve, 1-40wt% of binder and 1-90wt% of carrier; the molecular sieve is a modified Y-type molecular sieve and/or an unmodified Y-type molecular sieve; the binder is a silicon oxide binder and/or an aluminum oxide binder; the carrier can be one or more selected from silicon dioxide, kaolin, montmorillonite, diatomite, halloysite, soapstone, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
The method has strong raw material adaptability, and is not only suitable for light catalytic cracking raw materials such as hydrogenated LCO and the like, but also suitable for deep catalytic cracking process of low-quality heavy raw materials with high density and low hydrogen content. Optionally, the raw oil is at least one of unhydrogenated LCO, hydrogenated LCO, straight run diesel, coker diesel and hydrofined straight diesel.
Optionally, in the modified Y-type molecular sieve, the content of rare earth elements is 3-15wt% based on oxide, the content of sodium elements is 0.01-0.8wt% and the content of zinc elements is 0.2-4.5wt%; the rare earth element may be, but is not limited to, one or more of La, ce, pr, and Nd.
On the other hand, referring to fig. 1, the invention also provides a system for producing light olefins and aromatic hydrocarbons by catalytic cracking, which comprises a downstream bed reactor, a gas-solid rapid separation device, a stripper and a regenerator which are connected in sequence, wherein a discharge port of the regenerator is connected with a catalyst inlet of the fluidized bed reactor; wherein, the side wall of the inlet of the downer reactor is tangentially provided with a rotational flow air inlet. The system is particularly suitable for the catalytic cracking method for producing the low-carbon olefin and the aromatic hydrocarbon.
Wherein, 2-6 swirl inlets, preferably 2 swirl inlets, can be arranged on one downer reactor; the swirl inlet is lower than the inlet of the raw oil.
The system also comprises a cyclone separator, wherein a feed inlet of the cyclone separator is communicated with a lateral discharge outlet of the gas-solid rapid separation device, a solid-phase discharge outlet of the cyclone separator is communicated with the stripper, and a stripping outlet of the stripper is communicated with the feed inlet of the cyclone separator.
Optionally, wherein the aspect ratio of the downer reactor is from 2 to 50:1, preferably 5-20:1.
according to a particularly preferred embodiment of the invention, referring to fig. 1-3, the catalyst enters the top end of the downer reactor 7 through the spent slide valve 3, the first fluidizing medium enters the top end of the downer reactor, the raw oil enters the top end of the downer reactor 7 through the oil inlet nozzle 4 after being preheated, the first fluidizing material moving downwards is obtained, and the second fluidizing medium is introduced into the downer reactor 7 through the cyclone air inlet 6 tangentially so as to drive the first fluidizing material to perform catalytic cracking reaction under the state of cyclone and flowing downwards. The reaction product oil gas and the catalyst are separated at the bottom of the downer reactor 7 through a gas-solid rapid separation device 10, the separated side materials enter a cyclone separator 9 for separation again, the separated product oil gas enters a fractionation unit through a product oil gas discharge pipeline 8, and the catalyst separated through the cyclone separator 9 enters a stripper 14 through a catalyst pipeline 12 and is stripped by stripping steam 13. After the catalyst is stripped, the stripped oil gas enters the cyclone separator 9 through a stripping oil gas pipeline 11. The stripped catalyst enters a riser regenerator 17 through a regeneration slide valve 15, is introduced into a regeneration medium 16 for burning regeneration, is separated at a riser outlet cyclone 18 and is settled in a settler 19, and the regenerated flue gas is separated by a settler cyclone 20 and is discharged from a flue gas outlet pipeline 21. The regenerated catalyst enters the reactor from the spent slide valve 3 for the next cycle.
The invention is illustrated in further detail by the following examples. The starting materials used in the examples were all available commercially without any particular explanation.
The feedstock hydrogenated LCO properties used in the examples and comparative examples are shown in table 1.
TABLE 1
| Raw oil name | Hydrogenated LCO |
| Density (20 ℃ C.) kg/m 3 | 888.7 |
| Carbon content, weight% | 88.37 |
| Hydrogen content, wt% | 11.63 |
| Hydrocarbon group mass composition | |
| Paraffin, weight% | 13.0 |
| Total cycloalkane | 34.4 |
| Total aromatic hydrocarbon | 52.6 |
| Colloid, weight percent | 0 |
| Total weight, weight percent | 100 |
The catalysts SLA-10 used in the examples and comparative examples were identical and the catalyst properties are shown in Table 2 and were prepared as follows: (1) Ion exchange is carried out on the NaY molecular sieve and rare earth salt solution (cerium nitrate), the temperature is 40 ℃, the time is 100 minutes, and the mass ratio of the NaY molecular sieve to the rare earth salt to the solvent water is 1:0.1:10; the mass of the NaY molecular sieve and the rare earth salt are calculated according to dry basis and rare earth oxide respectively. (2) The ion-exchanged molecular sieve was calcined at 400 c in an atmosphere having a water vapor content of 40% by volume for 6 hours. (3) Reacting the roasted molecular sieve with silicon tetrachloride at the temperature of 500 ℃ for 3 hours, wherein the mass ratio of the silicon tetrachloride to the roasted molecular sieve is 0.5:1, the mass of the molecular sieve after roasting is calculated on a dry basis. (4) The molecular sieve is impregnated with zinc salt solution (zinc nitrate), the impregnated molecular sieve is roasted at 40 ℃, the roasting temperature is 500 ℃, the roasting time is 3 hours, and the modified Y molecular sieve is obtained, wherein the rare earth element (Ce) content is 9wt%, the sodium element content is 0.5wt% and the zinc element content is 2wt%. (5) The catalyst was prepared by slurrying 15wt% modified Y molecular sieve, 10wt% binder (silica binder), 70wt% carrier (kaolin clay) and water (solids content 40 wt%), and spray drying.
TABLE 2
| Catalyst numbering | SLA-10 |
| Microreaction Activity | 75 |
| Specific surface area, rice 2 Gram/gram | 124 |
| Pore volume, ml/g | 0.26 |
| Sieving to obtain the final product with weight percentage | |
| 0-40 micrometers | 11.8 |
| 40-80 micrometers | 53.2 |
| >80 micrometers | 35 |
Example 1
This example was tested according to the apparatus and procedure of fig. 1 in a small downer reactor with 1 set of swirl inlets (i.e., two in point symmetry), using hydrogenated LCO as feed oil in table 1, and on a downer reactor with SLA-10 catalyst, 75 catalyst activity and catalyst properties as listed in table 2. The reaction and regeneration process conditions are as follows: the preheating temperature of the hydrogenated LCO is 200 ℃, the reaction outlet temperature is 650 ℃, the reaction pressure is 0.2MPa, the catalyst-to-oil ratio is 20, and the residence time is 1.0Second, the gas linear velocity of the rotational flow is 4m/s, and the gas angular velocity is 2s -1 The regenerator outlet temperature was 700 ℃, the regenerator pressure was 0.6MPa, the regenerator medium was air, and the weight ratio of water vapor to total feedstock was 0.15.
The catalyst enters the top end of the downer reactor through a waiting slide valve, a first fluidizing medium enters the top end of the downer reactor, raw oil enters the top end of the downer reactor through an oil inlet nozzle after being preheated, a first fluidizing material moving downwards is obtained, and a second fluidizing medium is introduced into the downer reactor through a rotational flow air inlet tangentially so as to drive the first fluidizing material to achieve rotational flow and to perform catalytic cracking reaction under the downward flowing state. The reaction product oil gas and the catalyst are separated at the bottom of the descending bed through a gas-solid rapid separation device, the separated lateral materials enter a cyclone separator for re-separation, the separated product oil gas enters a fractionation unit through a product oil gas discharge pipeline, and the catalyst separated through the cyclone separator enters a stripper for stripping through stripping gas. After the catalyst is stripped, the stripped oil gas enters the cyclone separator through a stripped oil gas pipeline. The stripped catalyst enters a riser regenerator through a regeneration slide valve to carry out coke burning regeneration, is separated in a riser outlet cyclone separator and is settled in a settler, and the regenerated flue gas is separated through the settler cyclone separator and is discharged from a flue gas outlet pipeline. The regenerated catalyst enters the reactor from the spent slide valve and is subjected to the next cycle. The operating conditions and products are listed in Table 3, respectively.
Example 2
Catalytic cracking was performed as in example 1, except that the swirl inlets were 3 groups (i.e., six in point symmetry), and the oil and gas residence time was 2.0s. The operating conditions and products are listed in Table 3, respectively.
Comparative example 1
This comparative example uses the existing conventional riser catalytic cracking process, the reaction is carried out in a small riser reactor, and the non-hydro mode of operation, catalyst and feedstock, are the same as in example 1. The reaction and regeneration process conditions are as follows: the hydrogenation LCO preheating temperature is 200 ℃, the reaction outlet temperature is 550 ℃, the reaction pressure is 0.2MPa, the catalyst-oil ratio is 10, the residence time is 3.5 seconds, the linear velocity of the fluidized gas is 4m/s, the outlet temperature of the regenerator is 700 ℃, the pressure of the regenerator is 0.6MPa, the pressure of the regenerator is air, and the weight ratio of water vapor to total raw materials is 0.15. The operating conditions and product distribution are listed in Table 3.
Comparative example 2
This comparative example used the conventional downer catalytic cracking process, the reaction was carried out in a small downer reactor, and the catalyst and feedstock were catalytically cracked in the same manner as in example 1, using the non-hydrogen operating mode, as in example 1, except that no swirl inlet was provided, no swirl fluidizing medium was provided, and the oil and gas residence time was 0.7s. The operating conditions and products are listed in Table 3, respectively.
TABLE 3 Table 3
| Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | |
| Raw oil | Hydrogenated LCO | Hydrogenated LCO | Hydrogenated LCO | Hydrogenated LCO |
| Reaction mode | Lifting pipe | Descending bed | Descending bed | Descending bed |
| Swirl air inlet | Without any means for | Without any means for | Group 1 | Group 3 |
| Catalyst name | SLA-10 | SLA-10 | SLA-10 | SLA-10 |
| Catalyst Activity (MAT) | 75 | 75 | 75 | 75 |
| Reaction operating conditions | ||||
| Reaction pressure, MPa | 0.2 | 0.4 | 0.4 | 0.4 |
| Outlet temperature of reaction zone, DEG C | 550 | 650 | 650 | 650 |
| Catalyst to raw oil weight ratio | 10 | 20 | 20 | 20 |
| Residence time of oil and gas, s | 3.5 | 0.7 | 1.0 | 1.5 |
| Product yield, weight% | ||||
| Dry gas | 5.09 | 5.5 | 5.70 | 6.1 |
| Liquefied gas | 14.27 | 15.61 | 17.68 | 18.27 |
| Gasoline | 41.18 | 43.25 | 44.25 | 45.79 |
| Diesel oil | 28.92 | 26.62 | 23.92 | 21.84 |
| Slurry oil | 2.06 | 1.98 | 1.96 | 1.84 |
| Coke | 8.48 | 7.04 | 6.49 | 6.16 |
| Totalizing | 100 | 100 | 100 | 100 |
| Ethylene + propylene + butene | 7.14 | 10.76 | 12.25 | 14.51 |
| BTX | 15.32 | 17.24 | 19.59 | 21.46 |
As can be seen from table 3, the triene yield and BTX yield were high in examples 1 and 2 as compared with comparative examples 1 and 2. The results show that the cyclone downer reactor with high temperature and large catalyst-to-oil ratio is adopted, and the cyclone downer reactor has higher yield of low-carbon olefin and aromatic hydrocarbon. By strengthening the gas-solid contact efficiency, the advantage of high severity is fully exerted, and the selectivity of the product is increased.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A method for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking is characterized by comprising the following steps: enabling a first fluidizing medium, a catalyst and raw oil to enter the top end of a downer reactor and to perform first fluidization to obtain a first fluidizing material moving downwards; and introducing a second fluidizing medium tangentially into the downer reactor through a cyclone air inlet to drive the first fluidizing material to perform catalytic cracking reaction under the state of cyclone flow and downward flow, then performing gas-solid separation and steam stripping to obtain a spent catalyst and reaction product oil gas, and regenerating the spent catalyst and returning the spent catalyst to perform the catalytic cracking reaction.
2. The method of claim 1, wherein one of said downer reactors has 2-6 of said cyclone inlets disposed thereon; the rotational flow air inlet is lower than the inlet of the raw oil;
the weight flow ratio of the first fluidizing medium to the second fluidizing medium is 0.01-1:1.
3. a method according to claim 1 or 2, wherein the gas linear velocity of the swirling flow is 0.1-10m/s, preferably 1-5m/s; the gas angular velocity of the rotational flow is 0.01-10s -1 Preferably 0.1 to 5s -1 。
4. The process of claim 1 or 2, wherein the downer reactor has an aspect ratio of 2-50:1, preferably 5-20:1, a step of;
the conditions of the catalytic cracking include: the reaction temperature is 500-800 ℃, preferably 560-690 ℃; the reaction pressure is 0.1-2.0MPa, preferably 0.3-1MPa; the weight ratio of the agent to the oil is 10-150, preferably 15-50; the residence time is from 0.2 to 10 seconds, preferably from 0.5 to 5 seconds.
5. The method according to claim 1 or 2, wherein the fluidizing medium is steam and/or dry gas;
the catalyst comprises 10-60wt% of molecular sieve, 1-40wt% of binder and 1-90wt% of carrier; the molecular sieve is a modified Y-type molecular sieve and/or an unmodified Y-type molecular sieve; the binder is selected from a silicon oxide binder and/or an aluminum oxide binder; the carrier is at least one selected from one or more of silicon dioxide, kaolin, montmorillonite, diatomite, halloysite, soapstone, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite;
the raw oil is at least one of unhydrogenated LCO, hydrogenated LCO, straight-run diesel, coked diesel and hydrofined diesel.
6. The method according to claim 5, wherein the modified Y-type molecular sieve has a rare earth element content of 3 to 15wt%, a sodium element content of 0.01 to 0.8wt%, and a zinc element content of 0.2 to 4.5wt%, in terms of oxide; the rare earth element is one or more of La, ce, pr and Nd.
7. The system for producing the low-carbon olefin and the aromatic hydrocarbon by catalytic cracking is characterized by comprising a downstream bed reactor, a gas-solid rapid separation device, a stripper and a regenerator which are connected in sequence, wherein a discharge port of the regenerator is connected with a catalyst inlet of the fluidized bed reactor; wherein, the side wall of the inlet of the downer reactor is tangentially provided with a rotational flow air inlet.
8. The system of claim 7, wherein one of said downer reactors has 2-6 of said cyclone inlets disposed thereon; the swirl inlet is lower than the inlet of the raw oil.
9. The system of claim 7 or 8, further comprising a cyclone, wherein a feed inlet of the cyclone is in communication with a side discharge outlet of the gas-solid rapid separation device, a solid phase discharge outlet of the cyclone is in communication with the stripper, and a stripping outlet of the stripper is in communication with the feed inlet of the cyclone.
10. The system of claim 7 or 8, wherein the downer reactor has an aspect ratio of 2-50:1, preferably 5-20:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210794829.8A CN117384665A (en) | 2022-07-05 | 2022-07-05 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210794829.8A CN117384665A (en) | 2022-07-05 | 2022-07-05 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117384665A true CN117384665A (en) | 2024-01-12 |
Family
ID=89439776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210794829.8A Pending CN117384665A (en) | 2022-07-05 | 2022-07-05 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117384665A (en) |
-
2022
- 2022-07-05 CN CN202210794829.8A patent/CN117384665A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103131464B (en) | A kind of hydrocarbons catalytic conversion method producing low-carbon alkene and light aromatic hydrocarbons | |
| CN103131463B (en) | Hydrocarbon catalytic conversion method for increasing propylene yield | |
| CN101440014B (en) | Method for producing light olefins | |
| CN109705905B (en) | Method and device for producing more low-carbon olefins | |
| CN101456783B (en) | Method for improving light olefins output during catalytic cracking process | |
| CN103664444A (en) | Method of producing ethylene and propylene by using waste catalytic cracking catalyst | |
| CN112680248B (en) | Catalytic conversion method and device for producing more light olefins | |
| CN105461497B (en) | The two-stage regeneration reaction unit and its reaction method of methanol and/or dimethyl ether conversion producing light olefins and aromatic hydrocarbons | |
| CN112680247B (en) | Catalytic conversion method and device for increasing yield of low-carbon olefins | |
| CN112745926A (en) | Method and system for treating catalytic pyrolysis gasoline, and process and device for producing light olefins and light aromatics in high yield | |
| CN117384665A (en) | Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking | |
| CN110724553A (en) | Method and system for catalytic cracking by adopting dilute phase conveying bed and rapid fluidized bed | |
| CN113735676B (en) | Method for high-selectivity catalytic pyrolysis of high-yield propylene and high-yield gasoline | |
| CN111606771B (en) | Methanol and light hydrocarbon coupling cracking device and method | |
| CN117384663A (en) | Method and system for producing low-carbon olefin and aromatic hydrocarbon by downstream catalytic cracking | |
| CN117384664A (en) | Method and system for producing low-carbon olefin and aromatic hydrocarbon by vortex catalytic cracking | |
| CN117384662A (en) | Method and system for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking in cyclone reactor | |
| CN114763485B (en) | Catalytic conversion method for preparing ethylene and propylene | |
| CN112723971A (en) | Method for producing ethylene and propylene from carbon-tetrahydrocarbon | |
| CN115725326B (en) | Catalytic conversion method and device for producing ethylene, propylene and light aromatic hydrocarbon | |
| CN115028507B (en) | Catalytic conversion method for maximizing ethylene production and propylene production | |
| CN114763488B (en) | Catalytic conversion method for preparing low-carbon olefin | |
| CN116059934B (en) | System and method for preparing low-carbon olefin and aromatic hydrocarbon by processing LCO | |
| CN115895710B (en) | Catalytic conversion method and device for producing low-carbon olefin | |
| CN110724551B (en) | Method and system for catalytic cracking by adopting dilute phase conveying bed and turbulent fluidized bed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |