CN109575982A - A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons - Google Patents
A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons Download PDFInfo
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- CN109575982A CN109575982A CN201811190135.3A CN201811190135A CN109575982A CN 109575982 A CN109575982 A CN 109575982A CN 201811190135 A CN201811190135 A CN 201811190135A CN 109575982 A CN109575982 A CN 109575982A
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- CN
- China
- Prior art keywords
- crude oil
- aromatic hydrocarbons
- carbon olefin
- preparing low
- catalytically cracking
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- 239000010779 crude oil Substances 0.000 title claims abstract description 35
- 238000005336 cracking Methods 0.000 title claims abstract description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000010612 desalination reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 239000000470 constituent Substances 0.000 claims abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 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 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004230 steam cracking Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 19
- 238000007233 catalytic pyrolysis Methods 0.000 description 17
- 238000004523 catalytic cracking Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- -1 cycloalkanes aromatic hydrocarbon Chemical class 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000003134 recirculating effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/847—Vanadium, niobium or tantalum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons, which comprises the following steps: 1) crude oil is after desalination, dehydration, into heating stove heating, then into destilling tower, crude oil is divided into weight component, cut point is between 150~300 DEG C；2) heavy constituent that the light component and tower bottom that tower top comes out come out is reacted in two reactors, the light component, that is, Light feeds and the heavy constituent, that is, heavy feedstocks respectively in two reactors under water vapour atmosphere with high temperature catalyst haptoreaction.Compared with prior art, the method for crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons provided by the invention has the advantage that 1) adaptability to raw material is strong；2) catalyst anti-metallic contamination ability is strong, and hydrothermal deactivation will not occur, and agent consumption is low；3) compared with steam cracking, low energy consumption；4) conversion per pass is high, alkene selectivity is high.
Description
Technical field
The present invention relates to petrochemical industry more particularly to a kind of sides of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons
Method.
Background technique
The fast development of new-energy automobile constantly squeezes the market space of conventional fuel oil automobile, this directly affects product oil
Market.For the development for complying with situation, refine oil imperative to chemical industry transition.
Deep catalytic cracking technology can be ideal refinery by the alkene of C4 or more, heavy oil conversion at ethylene and propylene
Integrated technique.However there is also limitations for the technology.First is that current deep catalytic cracking technology is not capable of processing tenor height
Residual oil, especially measure high residual oil containing vanadium (V), when its content is more than 1 μ g/g, the molecular sieve active component of catalyst will be by
It is destroyed to apparent；Another limitation is that C8 alkane cracking conversion ratio below and olefine selective be not high.
It is not capable of processing tenor height in order to solve deep catalytic cracking technology, is not capable of processing asking for the residual oil containing V especially
Topic, China Petroleum Univ. (East-China) develop wax tailings, coker gasoline deep catalytic cracking technology, can be by wax tailings and coking
Gasoline be converted at low cost the high value added products such as propylene, isobutene, high-knock rating gasoline and diesel oil (Li Chunyi etc.,
200910229606.1；Gao Chuancheng, Li Chunyi etc., petrochemical technology and application, 2015,33 (1): 59-63).Wax tailings catalysis
Cracking, solves the problems, such as the cycloalkanes fragrance hydrocarbon pyrolysis, it means that the height that other fragrance in addition to wax tailings divide content high
Density wax oil can also be processed using the technology.But the technology not can solve the cracking problem of condensed-nuclei aromatics.For
This, China Petroleum Univ. (East-China) in CN200910229606.1, CN201210313281.7, CN201010166878.4 and
On the basis of the patents such as CN201310072027.7, it is further proposed that catalytic pyrolysis is formed group technology with hydrogen is added, it will be catalyzed
The high density diesel oil and recycle oil that cracking reaction generates add hydrogen, and condensed-nuclei aromatics therein is converted to cycloalkane or cycloalkanes aromatic hydrocarbon
Catalytic pyrolysis freshening is returned again, and the condensed-nuclei aromatics that cannot be cracked is converted to the aromatic hydrocarbons of alkene and gasoline fraction in this way.
The core technology thought of these patents is two-phase transportation bed reactor, is remarkably improved contact of the oil gas with catalyst
Efficiency promotes catalytic cracking reaction.
The catalytic pyrolysis of straight-run naphtha has multinomial patent to propose different solutions from catalyst to reactor.
Patent CN201510296090.8 proposes the method that steam cracking is combined with catalytic pyrolysis, converts naphtha into alkene, virtue
Hydrocarbon and high-knock rating gasoline.Into catalytic cracking reaction device, the small molecule alkane which generates divides for naphtha and macromolecular alkene
It separates out and carrys out laggard steam cracking.Patent CN201310521886.X proposition uses fixed bed reactors, with the molecule of MWW structure
Sieve the naphtha catalytic cracking scheme that (MCM-22) is catalyst activity component, naphtha elder generation dealkalize nitrogen, then in water vapour
Participate in lower progress catalytic pyrolysis.The scheme that patent CN201110375191.6 is proposed is reacted again using riser recirculating fluidized bed
Raw system carries out naphtha catalytic cracking, and wherein after the catalyst coke burning regeneration of carbon deposit, a part directly returns riser reactor,
Another part participates in catalysis reaction into riser again after going to duct modified region to contact progress duct modification with duct dressing agent.The party
Method not only has catalytic pyrolysis effect to C4-C8 alkene, can be also used for the catalytic pyrolysis of heavy oil.Patent CN201310389813
It proposes the raw material that straight-run diesel oil etc. is high containing alkane, catalytic pyrolysis is carried out using reaction-regeneration system similar with catalytic cracking.Specially
Sharp CN201410408704.2 equally uses the reaction-regeneration system of similar catalytic cracking, and but, raw material is other than light oil, it is also necessary to
Subregion injects carbon dioxide.Patent CN201110317870.8 equally uses riser recirculating fluidized bed reaction-regeneration system, carries out light
Riser is placed in the inside of regenerator to reduce energy consumption by the catalytic pyrolysis of hydrocarbon.Patent CN201310485219.0 is proposed
The catalytic pyrolysis generation for carrying out heavy oil and lighter hydrocarbons using the recirculating fluidized bed of modified beta-molecular sieve catalyst, three reactors is low
Carbon olefin and light aromatic hydrocarbons.Patent CN201480024324.7 propose catalyst molecular sieve active component need containing barium, strontium,
One or more of titanium and tungsten.Yao Hui etc. (Industrial Catalysis, 2006,14 (3): 11-13) has studied naphtha and aoxidizes in metal
On object catalyst under conditions of 700 DEG C, water-oil factor 3/1 catalytic pyrolysis, yield of ethene nearly 33%.Patent
CN201410411692.9 proposes naphtha in the first reaction zone and catalyst haptoreaction area, and the C4 rich in alkene is at second
The mixture of reaction zone and catalyst haptoreaction, this two strands of oil gas and catalyst converges to enters the higher third of temperature together
Reaction zone continues to react.The naphtha catalytic cracking reactor that patent CN201010208217.3 is proposed, in riser on
Portion has extension diameter section, and naphtha is contacted and reacted with high temperature regeneration agent in promotion bottom of the tube, flows up to riser middle and upper part
Extension diameter section, then mixed with the catalyst to come from settler and continue up flowing, into settler.Patent
CN200610027910.4 proposes to improve naphtha catalytic pyrolysis catalyst using ZSM-5/ mordenite composite molecular sieve
Activity.
The present invention is in the two-phase transportation bed reactor for generating low-carbon alkene for heavy oil catalytic pyrolysis proposed originally
On the basis of, the solution that low-carbon alkene proposes is generated for crude oil catalytic pyrolysis.
Summary of the invention
It is an object of the invention to crude oil is disposably passed through to Efficient Conversion into ethylene, propylene and aromatic hydrocarbons, specific offer
A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons, which comprises the following steps:
1) crude oil is divided into weight component then into destilling tower into heating stove heating, cut by crude oil after desalination, dehydration
O'clock between 150~300 DEG C；
2) recombination that the light component and tower bottom that tower top comes out come out respectively enters is reacted in two reactors.
Based on the above technical solution, the Light feeds and high-temperature regenerated catalyst carry out under water vapour atmosphere
Reaction, reaction temperature are 600~800 DEG C, preferably 670~760 DEG C；The matter of the reaction water vapour and Light feeds
The ratio between amount is 0.05:1~1:1, preferably 0.15:1~0.5:1.
Based on the above technical solution, the heavy feedstocks are reacted under water vapour atmosphere with catalyst,
Reaction temperature is 500~780 DEG C, preferably 580~700 DEG C；The mass ratio of the water vapour and heavy feedstocks is 0.05:
1~1:1, preferably 0.15:1~0.5:1.
Based on the above technical solution, two reactors are straight tube reactor, preferably bottom belt
There is the straight tube reactor of expanding close phase section.The reactor is the reactor with expanding close phase section, real by expanding reduction of speed
Existing dense fluidized.Charging sprays into close phase section, is conducive to charging and is adequately contacted, exchanged heat and reacted with catalyst, is conducive to
The high boiling difficult easy green coke component of cracking of Catalyst Adsorption, reduces the coking tendency of system.
Based on the above technical solution, mean residence time > 0.5s of the Light feeds in close phase section, preferably
Control between 1~2s；Total mean residence time is no more than 10s in reactor, is preferably no more than 6s.
Based on the above technical solution, mean residence time > 0.05s of the heavy feedstocks in close phase section, it is excellent
The control of choosing is between 0.2~2s；Total mean residence time is no more than 10s, preferably more than 5s in reactor.
Based on the above technical solution, linear velocity > 0.1m/s in the close phase section, preferred control 0.5~
Between 3m/s.
Based on the above technical solution, the catalyst is with SiO2And Al2O3The alumino-silicate of composition be mainly at
Point；Preferably also containing alkali metal oxide, alkaline earth oxide, the oxide of Ti, Fe, V and Ni oxide；More
Preferably, the alkali metal oxide is Na2O、K2One or both of O, the alkaline earth oxide are in CaO, MgO
One or two.The SiO2And Al2O3The silicate of composition, be partially one of molecular sieve, kaolin, mullite or
It is several, it is partially by SiO2Or its precursor silica solution and/or sodium metasilicate and Al2O3Precursor composition.
Based on the above technical solution, in terms of mass percentage, the SiO2Content be 30~80%, preferably
It is 40~60%；Al2O3Content is 10~70%, preferably 25~60%；The content of the alkali metal oxide is not more than
5%, preferably it is not more than 3%；The content of the alkaline earth oxide is not more than 5%, is preferably not more than 3%；The Ti,
The content of the oxide of Fe V and Ni, each autoxidisable substance is not more than 2%, preferably below 1%.
Compared with prior art, the method for crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons provided by the invention has following
Advantage:
1) adaptability to raw material is strong, is applicable not only to Light feeds, such as the catalytic pyrolysis of ethane, propane, butane and naphtha,
Heavy feedstocks are also applied for, such as the catalytic pyrolysis of diesel oil, wax oil and residual oil, crude oil can also carry out catalytic pyrolysis；
2) catalyst anti-metallic contamination ability is strong, and hydrothermal deactivation will not occur, and agent consumption is low；
3) compared with steam cracking, reaction temperature of the present invention is relatively low, steam consumption is relatively fewer, thus low energy consumption；
4) one way is almost cracked by alkane, the cycloalkane in Light feeds, and the saturation in heavy feedstocks point is almost
Cracking completely, thus conversion per pass is high.In pyrolysis product, other than it the aromatic hydrocarbons of ring-opening reaction cannot occur, primary product is
Ethylene, propylene and a small amount of butylene, wherein methane production is lower than naphtha steam cracking, and ethane is seldom.It is burnt for Light feeds
Charcoal yield is almost nil；For heavy feedstocks, coke yield is not more than 4%, thus the selectivity of alkene is high.
Detailed description of the invention
Fig. 1 is the process flow diagram that the heated furnace of crude oil after desalination is divided into weight component.
Fig. 2 is the schematic device for implementing the method for crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons provided by the invention；
Wherein 1/12-- pre-lift medium, 2/13-- pre-lift pipe, 3-- heavy feedstocks, the close phase section of 4/15-- reactor, 5/17-- are promoted
Pipe, 6-- oil gas, 7-- settler, 8-- stripping section, 9-- inclined tube to be generated and slide valve, 10/16-- regenerator sloped tube and slide valve, 11/
22-- stripping medium, 14-- Light feeds, 18-- cooling and washing medium, 19-- regenerator, 20-- regenerator settling section, 21--
Air, 23-- flue gas.
Specific embodiment
Combined with specific embodiments below, the present invention is described further:
Embodiment 1
Respectively with the Russian oil and Daqing crude oil progress reaction experiment after desalination, the main character of two kinds of crude oil such as table
Shown in 1.Before being reacted, air-distillation is respectively adopted and extracts light component (naphtha), initial boiling point~200 DEG C, wherein Russia
The naphtha that crude oil is extracted is 23wt%, and the naphtha that Daqing crude oil is extracted is 12wt%.
The main character of table 1. Russian oil and Daqing crude oil
Reaction carries out on circulating fluidized bed device, and reaction-regeneration system catalyst inventory is 30kg, catalyst regeneration temperature 800
℃。
It is had in close phase section reactor and is reacted at two using attached Light feeds shown in Fig. 2 and heavy feedstocks.Operate item
Part and distribution of reaction products are as shown in table 2.Catalyst oxide composition: SiO2/Al2O3/MgO/Fe2O3/Na2O/V2O5It is 51/
42/4/0.5/1.5/1 (wt%).720 DEG C of light feed riser pipe outlet temperature, 650 DEG C of heavy feed riser outlet temperature,
Two reactor water steam account for the 25wt% of oil inlet quantity.
As seen from Table 2, raw material conversion is very abundant, and gasoline, diesel oil and the remaining heavy oil of generation are essentially all cannot
The aromatic hydrocarbons cracked again.For ethylene+propylene yield, Russian oil is 46.56%, and Daqing crude oil is 47.45%.
The Light feeds (naphtha) and heavy feedstocks of 2. Russian oil of table and Daqing crude oil are urged in two reactors
Change cracking operation condition and product distribution
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons, which comprises the following steps:
1) crude oil is divided into weight component, cut point exists then into destilling tower into heating stove heating after desalination, dehydration by crude oil
Between 150~300 DEG C；
2) heavy constituent that the light component and tower bottom that tower top comes out come out is reacted in two reactors.
2. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 1, which is characterized in that institute
It states Light feeds and is reacted under water vapour atmosphere with high-temperature regenerated catalyst, reaction temperature is 600~800 DEG C；It is described
The mass ratio for reacting water vapour and Light feeds is 0.05:1~1:1.
3. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 1, which is characterized in that institute
It states heavy feedstocks and is reacted under water vapour atmosphere with catalyst, reaction temperature is 500~780 DEG C；The water vapour with
The mass ratio of heavy feedstocks is 0.05:1~1:1.
4. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 1 to 3, feature
It is, the reactor is straight tube reactor, preferably has the straight tube reactor of expanding close phase section.
5. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 4, which is characterized in that institute
State mean residence time > 0.5s of the Light feeds in close phase section；Total mean residence time is no more than 10s in reactor.
6. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 5, which is characterized in that institute
State mean residence time > 0.05s of the heavy feedstocks in close phase section；Total mean residence time is no more than 10s in reactor.
7. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 6, which is characterized in that institute
Average linear velocity > 0.1m/s in close phase section is stated, preferred control is between 0.5~3m/s.
8. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 1, which is characterized in that institute
Catalyst is stated with SiO2And Al2O3The alumino-silicate of composition is main component, also contains alkali metal oxide, alkaline-earth metal oxide
Object, the oxide of Ti, Fe, V and Ni oxide.
9. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 8, which is characterized in that with
Mass percentage meter, the SiO2Content be 30~80%；Al2O3Content is 10~70%, the alkali metal oxide
Content is not more than 5%；The content of the alkaline earth oxide is not more than 5%, and the oxide of the Ti, Fe V and Ni are each
The content of autoxidisable substance is not more than 2%.
10. the method for a kind of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons according to claim 9, which is characterized in that
The alkali metal oxide is Na2O、K2One or both of O, the alkaline earth oxide be one of CaO, MgO or
Two kinds；The SiO2And Al2O3The silicate of composition is partially one or more of molecular sieve, kaolin, mullite, part
It is by SiO2Or its precursor silica solution and/or sodium metasilicate and Al2O3Precursor composition.
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| CN114426875A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin and BTX by catalytic cracking of crude oil |
| CN114426875B (en) * | 2020-10-29 | 2023-07-11 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin and BTX by catalytic pyrolysis of crude oil |
| CN115322066A (en) * | 2021-05-11 | 2022-11-11 | 青岛京润石化设计研究院有限公司 | Method and device for preparing low-carbon olefin by catalytic conversion of crude oil |
| CN113462428B (en) * | 2021-07-07 | 2022-11-25 | 中国石油大学(华东) | Method for preparing chemicals through catalytic conversion of crude oil in double-pipe parallel multi-zone mode |
| CN113462428A (en) * | 2021-07-07 | 2021-10-01 | 中国石油大学(华东) | Method for preparing chemicals through double-pipe parallel multi-zone catalytic conversion of crude oil |
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