CN114456036A - Method for producing aromatic hydrocarbon and olefin - Google Patents
Method for producing aromatic hydrocarbon and olefin Download PDFInfo
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- CN114456036A CN114456036A CN202011140884.2A CN202011140884A CN114456036A CN 114456036 A CN114456036 A CN 114456036A CN 202011140884 A CN202011140884 A CN 202011140884A CN 114456036 A CN114456036 A CN 114456036A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 94
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 27
- 238000004230 steam cracking Methods 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 12
- 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 109
- 229910052751 metal Inorganic materials 0.000 claims description 95
- 239000002184 metal Substances 0.000 claims description 95
- 239000002808 molecular sieve Substances 0.000 claims description 79
- 230000002378 acidificating effect Effects 0.000 claims description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims description 35
- 150000004706 metal oxides Chemical class 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 28
- 238000005336 cracking Methods 0.000 claims description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229910052702 rhenium Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 238000004523 catalytic cracking Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 230000003100 immobilizing effect Effects 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 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 5
- -1 lanthanide metals Chemical class 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 238000001833 catalytic reforming Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 54
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 16
- 229910052680 mordenite Inorganic materials 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 11
- 239000011609 ammonium molybdate Substances 0.000 description 11
- 229940010552 ammonium molybdate Drugs 0.000 description 11
- 235000018660 ammonium molybdate Nutrition 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 238000010586 diagram Methods 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- 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
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
-
- 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
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- 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
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for producing aromatic hydrocarbon and olefin, which comprises the following steps: the mixed hydrocarbon raw material containing aromatic hydrocarbon enters an aromatization unit to contact and react with a catalyst of the aromatization unit, and reaction products are separated to obtain C5 ‑Component C6 +Preparing components; c6 +The components enter an alkyl transfer unit to be in contact reaction with an alkyl transfer catalyst, and a reaction product is separated to obtain C5 ‑Component C8 component comprising C6 +The remaining components of (a); the C8 component enters an aromatic hydrocarbon purification unit to separate high-purity C8 aromatic hydrocarbon and C5 ‑Component (A) and (B) comprises6 +The remaining components of (a); c5 ‑The components enter a steam cracking unit for steam cracking; comprising C6 +All or part of the remaining componentsAnd separately returned to the transalkylation unit. The method can effectively convert the poor gasoline components into aromatic hydrocarbons and olefins, and realize high-efficiency oiling conversion.
Description
Technical Field
The invention relates to a method for producing aromatic hydrocarbon and olefin.
Background
With the increasing importance on atmospheric environment protection, in recent years, new energy vehicles are rapidly developed and gradually replace traditional gasoline vehicles, and the demand for gasoline for vehicles is expected to decline in the future. Therefore, the diversified utilization of gasoline components will be an important issue. The gasoline mainly contains aromatic hydrocarbon, olefin and alkane, and can be used for producing aromatic hydrocarbon and olefin components through conversion between hydrocarbons.
Aromatic hydrocarbons and olefins are basic raw materials of petrochemical industry, and main products of the aromatic hydrocarbons are BTX (benzene, toluene and xylene), wherein para-xylene isomer in the xylene is the most main aromatic hydrocarbon product. The main products of olefins are ethylene and propylene, which are important basic materials for the synthesis of polymers. The production capacity of p-xylene, ethylene and propylene in China is insufficient, and a large amount of import is needed. Therefore, the ability to accelerate the supply of xylene, ethylene and propylene is of great importance to the development of the aromatic industry in China. In industrial equipment, naphtha is used as raw material, and the catalytic reforming is used to produce benzene, toluene, xylene and heavy aromatics, and the toluene/benzene and C9 are passed through transalkylation unit+A is converted into dimethylbenzene, so that the yield of the dimethylbenzene is effectively improved. The petroleum-based ethylene mainly takes naphtha, ethane, propane and other light hydrocarbons as raw materials, and ethylene and propylene are produced through a steam cracking process. For a long time, the production of aromatic hydrocarbon and olefin has the problem of raw material competition, and the realization of raw material diversification is an important measure for expanding the productivity and optimizing the structure.
The transalkylation reaction between aromatic hydrocarbons is mainly to convert benzene, toluene and heavy aromatic hydrocarbons into xylene, so as to realize the value-added utilization of products. The reaction is acid catalytic reaction, the active component is mainly acidic molecular sieve, and the industrial catalyst is generally acidic-hydrogenation metal bifunctional catalyst.
The aromatization technology is to produce aromatic hydrocarbon by olefin and alkane through a complex aromatization process, the aromatization raw materials are wide, comprise a catalytic cracking gasoline component, a hydrocracking gasoline component, a byproduct light hydrocarbon of an oil refining device, LPG and the like, and can be used as a technical means for increasing the yield of the aromatic hydrocarbon or high-octane gasoline. The aromatization product of the common aromatic hydrocarbon production increasing route mainly contains benzene, toluene, xylene, carbon nine and other aromatic hydrocarbons, and the defect is that a high-concentration xylene product cannot be directly produced.
CN101767035B discloses a catalyst for producing BTX aromatic hydrocarbon by catalytic cracking gasoline and a preparation method thereof, the catalyst comprises 0.05-2.0 wt% of VIII group noble metal, O.2-5.0 wt% of Zn, 0.2-5.0 wt% of Sn, 5.0-80 wt% of ZSM-5/ZSM-11 cocrystallized molecular sieve, has good aromatization activity, BTX selectivity and sulfur-resistant and olefin-resistant performances, and can be used for preparing aromatic hydrocarbon by catalytic cracking gasoline or straight-run gasoline or gasoline components such as blending coking and cracking.
CN1488724A discloses a catalyst for aromatization and modification of catalytic gasoline and a process thereof, relating to a process for producing low-sulfur and low-olefin clean gasoline by catalytic cracking gasoline and a catalyst used by the process, wherein the process adopts a hydrofining/aromatization combined process, wherein the aromatization adopts a small-grain hydrogen type molecular sieve catalyst comprising IA group metals, transition group metals and rare earth metal oxides, and the grain size of the molecular sieve is in the range of 20nm-800 nm. The technological process of treating FCC gasoline through hydrorefining/aromatization has short pore passage, proper acidity, less antiknock index loss and other advantages. The hydrogenation refining process removes the alkadiene which is easy to coke at high temperature, and improves the stability of the aromatization catalyst with octane number recovery function.
CN1844323A discloses a process and a catalyst for modifying FCC gasoline distillate and simultaneously producing low-carbon olefin, raw material FCC gasoline distillate is preheated to the reaction temperature and enters a reactor filled with a modified zeolite molecular sieve catalyst for gasoline distillate modification reaction, the reaction product is cooled and cooled for gas-liquid separation, the liquid product is a modified gasoline product, and the gas product is separated to obtain the low-carbon olefin product. The modified zeolite molecular sieve catalyst is prepared by treating zeolite molecular sieve with steam at 600-850 deg.C for 1-24 hr, and has the advantages of no olefin reduction of FCC gasoline, high yield of ethylene, propylene and other products, and high economical efficiency.
Disclosure of Invention
The invention aims to mainly solve the problems of single raw material for producing aromatic hydrocarbon and olefin, insufficient raw material diversification route and the like in the prior art, and provides a method capable of effectively converting poor-quality gasoline components into aromatic hydrocarbon and olefin and realizing efficient conversion of oil.
To achieve the foregoing object, the present invention provides a method for producing aromatic hydrocarbons and olefins, comprising:
I) the mixed hydrocarbon raw material containing aromatic hydrocarbon enters an aromatization unit to contact and react with a catalyst of the aromatization unit, and reaction products are separated to obtain C5 -Component C6 +Preparing components;
II) C in step I)6 +The components enter an alkyl transfer unit to be in contact reaction with an alkyl transfer catalyst, and a reaction product is separated to obtain C5 -Component C8Component (A) comprising C6 +The remaining components of (a);
III) step II) C8The components enter an aromatic hydrocarbon purification unit to separate high-purity C8 aromatic hydrocarbon and C5 -Component (A) and (B) comprises6 +The remaining components of (a);
IV) step I) C5 -Component(s) and/or C in step II)5 -Component(s) and/or C in step III)5 -The components enter a steam cracking unit for steam cracking;
v) step II) comprises C6 +And/or step III) comprises C6 +And the remaining components are returned, in whole or in part, to the transalkylation unit.
Preferably, the boiling range of the mixed hydrocarbon feedstock containing aromatic hydrocarbons in step I) is in the range of from 50 to 250 c, preferably the boiling range of the mixed hydrocarbon feedstock containing aromatic hydrocarbons is in the range of from 60 to 210 c.
Preferably, in step I), the aromatic hydrocarbon-containing mixed hydrocarbon feedstock has an aromatic hydrocarbon content of 10 to 100% by weight, preferably 20 to 80% by weight.
Preferably, in step I), the mixed hydrocarbon feedstock containing aromatic hydrocarbons is derived from catalytically cracked gasoline, hydrocracked gasoline, ethylene cracked gasoline, catalytically reformed gasoline, straight run gasoline, LPG or any mixture thereof.
Preferably, the transalkylation catalyst in step II) comprises an acidic molecular sieve component, an oxide promoter, a first metal and/or a first metal oxide, wherein the first metal is selected from one or more of group VB, VIB and VIIB, and a second metal and/or a second metal oxide, wherein the second metal is a metal component different from the first metal; the first metal and/or first metal oxide is/are immobilized on the acidic molecular sieve component.
Preferably, the first metal and/or the first metal oxide is/are immobilized on the acidic molecular sieve component by physical mixing and/or chemical bonding.
Preferably, the second metal and/or the second metal oxide is/are supported on the oxide assistant, preferably the second metal and/or the second metal oxide is/are supported on the oxide assistant by physical mixing and/or chemical bonding.
Preferably, the first metal and/or first metal oxide is/are immobilized on the acidic molecular sieve component by physical mixing and/or chemical bonding; and the second metal and/or the second metal oxide is/are immobilized on the oxide assistant by physical mixing and/or chemical bonding.
Preferably, the transalkylation catalyst is prepared by steps comprising: immobilizing a first metal and/or a first metal oxide on the acidic molecular sieve, and immobilizing a second metal and/or a second metal oxide on an oxide auxiliary agent; then kneading and molding the two.
Preferably, the acidic molecular sieve component is present in an amount of 40 to 90 wt%, the oxide promoter is present in an amount of 5 to 40 wt%, the first metal and/or first metal oxide is present in an amount of 0.01 to 20 wt%, and the second metal and/or second metal oxide is present in an amount of 0.01 to 20 wt%, based on 100 wt% of the catalyst.
Preferably, the acidic molecular sieve component is present in an amount of 50 to 80 wt.%, the oxide promoter is present in an amount of 10 to 30 wt.%, the first metal and/or first metal oxide is present in an amount of 0.05 to 18 wt.%, and the second metal and/or second metal oxide is present in an amount of 0.05 to 18 wt.%, based on 100 wt.% of the catalyst.
Preferably, the second metal is selected from one or more of group IA, IIA, IIIA, IVA, VA and lanthanide metals, preferably from one or more of Sr, Bi, Ce, Zr and Ge.
Preferably, the first metal is selected from one or more of Mo, Re and W, preferably the first metal is at least two of Mo, Re and W, mixed in a weight ratio of 0.1-10: 1; more preferably a combination of the three, and the weight ratio of Mo, Re and W is 1: 0.1-0.4: 0.1-0.6.
Preferably, the acidic molecular sieve component is selected from acidic molecular sieve components characterized by an eight-membered, ten-membered or twelve-membered ring pore structure; preferably at least one selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12 and Y molecular sieves.
Preferably, the oxide adjuvant is selected from one or more of alumina, silica, magnesia, titania and kaolin.
Preferably, the transalkylation catalyst is prepared by a process comprising:
(1) impregnating a first metal source solution into the acidic molecular sieve component source, and carrying out first heat treatment to obtain a first solid;
dipping a second metal source solution into an oxide auxiliary agent source, and performing second heat treatment to obtain a second solid;
(2) kneading the first solid and the second solid, and forming.
Preferably, in the step (1), the steps of the first heat treatment and the second heat treatment each include: firing or, drying and firing,
wherein the drying conditions include: the temperature is 50-200 ℃, and the time is 1-30 h;
wherein, the roasting conditions comprise: heat-treating for 1-30 hours at 300-700 ℃ in an oxygen-containing atmosphere; preferably, the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the air to the water vapor is 5-100: 1.
Preferably, the first metal source is a soluble compound containing group VB, VIB and VIIB metals; and/or the second metal source is a soluble compound containing a second metal; and/or the source of acidic molecular sieve component is selected from acidic molecular sieve components characterized by an eight-membered, ten-membered or twelve-membered ring pore structure; preferably at least one selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12 and Y molecular sieves.
Preferably, the oxide promoter source is selected from one or more of alumina, silica, magnesia, titania and kaolin.
Preferably, the operating conditions of the aromatization unit in step I) include: the aromatization unit catalyst is selected from one or more of Zn/ZSM-5, Mo/ZSM-5 and Mo-Zn/ZSM-5, the reaction temperature is 400--1。
Preferably, the operating conditions of the transalkylation unit in step II) include: the reaction temperature is 250 ℃ and 500 ℃, the reaction pressure is 1.5-6.5MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 0.5-5h-1。
Preferably, the aromatic hydrocarbon purification unit in the step III) is an aromatic hydrocarbon extraction separation unit or a non-aromatic selective cracking unit.
Preferably, the aromatic hydrocarbon extraction separation unit performs extraction separation by extractive distillation based on a sulfolane solvent.
Preferably, the operating conditions of the non-aromatic selective cracking unit include: the catalyst contains at least one of molecular sieves of ZSM-5, MCM-22, MOR and Beta, and can selectively contain metal components selected from VIB, VIIB and VIII groups; the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-3.0MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 1-15h-1。
Preferably, the operating conditions of the steam cracking unit in step IV) include: the temperature of the cracking reaction is 600-1000 ℃.
According to the method, the content of aromatic hydrocarbon in the reaction product of the aromatization unit is increased by more than 10% compared with that of the raw material in percentage by weight, and in the optimized scheme, the content of aromatic hydrocarbon in the reaction product is increased by more than 20% compared with that of the raw material. The xylene content in the reaction product of the transalkylation unit is increased by more than 10 percent compared with the raw material in terms of weight percentage, and in the optimized scheme, the xylene content in the reaction product is increased by more than 25 percent compared with the raw material. The C8 product purification unit is an aromatic hydrocarbon extraction separation or non-aromatic selective cracking unit, and the purity of the purified C8 aromatic hydrocarbon product is higher than 99%.
In the invention, the hydrocarbon raw material containing aromatic hydrocarbon is subjected to aromatization unit to convert part of olefin and alkane into aromatic hydrocarbon products, and then is subjected to transalkylation unit to convert benzene, toluene and C9 +Conversion of aromatics to C-octa-aromatics with simultaneous cracking of non-aromatics to C2-C5Alkane is used as a high-quality ethylene cracking raw material; finally, the carbon octaarene is further purified by an arene extraction or non-arene cracking unit to obtain a high-purity carbon octaarene product and a byproduct C5 -The light component is used as high-quality ethylene cracking raw material. The process can effectively convert the poor gasoline components into aromatic hydrocarbons and olefins, and realize efficient oiling conversion.
In the preferred embodiment of the invention, the catalyst of the invention can further improve the yield of the carbon octaarene and the selectivity of the C2-C3 olefin.
Drawings
FIG. 1 is a schematic flow diagram of a method according to an embodiment of the invention;
fig. 2 is a schematic flow diagram of a method according to an embodiment of the invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for producing aromatic hydrocarbon and olefin, which comprises the following steps:
I) the mixed hydrocarbon raw material containing aromatic hydrocarbon enters an aromatization unit to contact and react with a catalyst of the aromatization unit, and reaction products are separated to obtain C5 -Component C6 +Preparing components;
II) C in step I)6 +The components enter an alkyl transfer unit to be in contact reaction with an alkyl transfer catalyst, and a reaction product is separated to obtain C5 -Component C8Composition, bagDraw C6 +The remaining components of (a);
III) step II) C8The components enter an aromatic hydrocarbon purification unit to separate high-purity C8 aromatic hydrocarbon and C5 -Component (A) and (B) comprises6 +The remaining components of (a);
IV) step I) C5 -Component and/or C in step II)5 -Component(s) and/or C in step III)5 -The components enter a steam cracking unit for steam cracking;
v) step II) comprises C6 +And/or step III) comprises C6 +And the remaining components are returned, in whole or in part, to the transalkylation unit.
In the present invention, C5 -Component C comprises5And the following components, C6 +Component C comprises6And the above components.
In the present invention, the high purity C8 aromatic hydrocarbon means that the purity of the aromatic hydrocarbon reaches or exceeds the purity requirement of a para-xylene adsorption separation or para-xylene crystallization separation unit on a C8 aromatic hydrocarbon raw material, for example, the purity is higher than 99%.
In the invention, the hydrocarbon raw material containing aromatic hydrocarbon is subjected to aromatization unit to convert part of olefin and alkane into aromatic hydrocarbon products, and then is subjected to transalkylation unit to convert benzene, toluene and C9 +Conversion of aromatics to C-octa-aromatics with simultaneous cracking of non-aromatics to C2-C5Alkane is used as a high-quality ethylene cracking raw material; finally, the carbon octaarene is further purified by an arene extraction or non-arene cracking unit to obtain a high-purity carbon octaarene product and a byproduct C5 -The light component is used as high-quality ethylene cracking raw material. The process can effectively convert the poor gasoline components into aromatic hydrocarbons and olefins, and realize efficient oiling conversion.
According to a preferred embodiment of the invention, the mixed hydrocarbon feedstock containing aromatic hydrocarbons in step I) has a boiling range of from 50 to 250 c, preferably a boiling range of from 60 to 210 c.
According to a preferred embodiment of the present invention, in step I), the aromatic hydrocarbon-containing mixed hydrocarbon feedstock has an aromatic hydrocarbon content of 10 to 100% by weight, preferably 20 to 80% by weight.
According to a preferred embodiment of the invention, in step I), the sulfur content of the aromatic-containing mixed hydrocarbon feedstock is from 3 to 6ppm by weight.
According to a preferred embodiment of the invention, in step I), the nitrogen content of the aromatic-containing mixed hydrocarbon feedstock is from 1 to 3ppm by weight.
According to a preferred embodiment of the invention, in step I), the olefin content in the mixed hydrocarbon feedstock containing aromatic hydrocarbons is from 20 to 45% by weight.
According to a preferred embodiment of the invention, in step I), the paraffinic hydrocarbon feedstock containing aromatic hydrocarbons comprises from 35 to 45% by weight of paraffinic hydrocarbons.
According to a preferred embodiment of the present invention, in step I), the mixed hydrocarbon feedstock containing aromatic hydrocarbons is derived from catalytically cracked gasoline, hydrocracked gasoline, ethylene cracked gasoline, catalytically reformed gasoline, straight run gasoline, LPG or any mixture thereof in step I).
The above-mentioned preferred raw materials can be efficiently used by being treated by the method of the present invention.
In the present invention, the transalkylation catalyst may be conventionally selected, and may for example be a catalyst comprising at least one first component selected from ZSM-5, ZSM-12, MOR, Beta, and at least one second component selected from Pt, Mo, Re.
According to a preferred embodiment of the present invention, the transalkylation catalyst comprises an acidic molecular sieve component, an oxide promoter, a first metal selected from one or more of group VB, VIB and VIIB, and/or a first metal oxide, and a second metal, which is a different metal component from the first metal, and/or a second metal oxide, the first metal and/or the first metal oxide being supported on the acidic molecular sieve component. The invention uses VB, VIB and VIIB group metals as active metal components of the transalkylation catalyst, and has the advantages of high reaction activity, low aromatic hydrocarbon loss and the like.
According to a preferred embodiment of the present invention, the first metal and/or the first metal oxide is/are immobilized on the acidic molecular sieve component by physical mixing and/or chemical bonding.
According to a preferred embodiment of the present invention, the second metal and/or the second metal oxide is/are supported on the oxide assistant, preferably the second metal and/or the second metal oxide is/are supported on the oxide assistant by physical mixing and/or chemical bonding.
According to a preferred embodiment of the present invention, the first metal and/or first metal oxide is/are immobilized on the acidic molecular sieve component by physical mixing and/or chemical bonding; and the second metal and/or the second metal oxide is/are immobilized on the oxide assistant by physical mixing and/or chemical bonding.
According to a preferred embodiment of the present invention, the transalkylation catalyst is prepared by: immobilizing a first metal and/or a first metal oxide on the acidic molecular sieve, and immobilizing a second metal and/or a second metal oxide on an oxide auxiliary agent; then kneading and molding the two.
In the invention, the distribution of the supported metal on the catalyst is regulated and controlled based on the influence of different hydrogenation metal components on the conversion reaction process of aromatic hydrocarbon, wherein the metal with higher hydrogenation function is supported on the surface of the molecular sieve to play a role in promoting the conversion efficiency of aromatic hydrocarbon, and the metal is supported on the oxide auxiliary agent to inhibit the side reaction of aromatic hydrocarbon hydrogenation saturation on the surface of the oxide auxiliary agent. Thereby greatly improving the conversion efficiency of the transalkylation catalyst for the conversion reaction of aromatic hydrocarbon and the selectivity of target products.
The invention adopts VB, VIB and VIIB group metals as active metal components of the transalkylation catalyst, and researches show that a better catalytic effect can be achieved by optimizing the microscopic distribution of the metals on the catalyst and combining the advantages of different metals, so that on one hand, the high-efficiency conversion of aromatic hydrocarbon can be realized, and simultaneously, the hydrogenation saturation of the aromatic hydrocarbon can be reduced. The metal loaded on the molecular sieve adopts a stronger hydrogenation function, and the metal loaded on the binder can inhibit the aromatic hydrocarbon hydrogenation saturation side reaction on the surface of the metal, so that the distribution can effectively improve the conversion efficiency of the molecular sieve and simultaneously reduce the aromatic hydrocarbon hydrogenation saturation side reaction.
In the present invention, the composition of the transalkylation catalyst can be selected in a wide range, and for the purposes of the present invention, it is preferred that the acidic molecular sieve component is present in an amount of 40 to 90 wt%, the oxide promoter is present in an amount of 5 to 40 wt%, the first metal and/or the first metal oxide is present in an amount of 0.01 to 20 wt%, and the second metal and/or the second metal oxide is present in an amount of 0.01 to 20 wt%, based on 100 wt% of the catalyst.
According to a preferred embodiment of the present invention, the acidic molecular sieve component is present in an amount of 50 to 80 wt.%, the oxide promoter is present in an amount of 10 to 30 wt.%, the first metal and/or first metal oxide is present in an amount of 0.05 to 18 wt.%, and the second metal and/or second metal oxide is present in an amount of 0.05 to 18 wt.%, based on 100 wt.% of the transalkylation catalyst.
According to the present invention, the second metal can be selected from a wide variety of metals, and hydrogenation metals other than the first metal can be used in the present invention, and for the present invention, the second metal is preferably selected from one or more of group IA, IIA, IIIA, IVA, VA and lanthanide metals, and more preferably from one or more of Sr, Bi, Ce, Zr and Ge.
According to the present invention, a first metal satisfying the aforementioned requirements of the present invention may be used in the present invention, and according to a preferred embodiment of the present invention, the first metal is selected from one or more of Mo, Re and W. According to a preferred embodiment of the present invention, it is preferred that the first metal is at least two of Mo, Re and W in a weight ratio of 0.1-10: 1; more preferably a combination of the three, and the weight ratio of Mo, Re and W is 1: 0.1-0.4: 0.1-0.6.
According to the invention, the variety of the acidic molecular sieve component can be selected from a wide range, the commonly used acidic molecular sieve component can be used in the invention, and the acidic molecular sieve component with the structural characteristics of eight-membered ring, ten-membered ring or twelve-membered ring is preferably selected in the invention; preferably at least one selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12 and Y molecular sieves.
According to the present invention, the kind of the oxide assistant is widely selectable, and a common oxide assistant may be used in the present invention, and for the present invention, one or more selected from the group consisting of alumina, silica, magnesia, titania and kaolin is preferable.
Catalysts meeting the aforementioned requirements of the present invention can be used in the present invention without particular requirements for the preparation process thereof, and according to a preferred embodiment of the present invention, there is provided a process for preparing the catalyst of the present invention, which comprises: (1) impregnating a first metal source solution with the acidic molecular sieve component source, and carrying out first heat treatment to obtain a first solid; dipping a second metal source solution into an oxide auxiliary agent source, and performing second heat treatment to obtain a second solid; (2) kneading the first solid and the second solid, and forming.
According to a preferred embodiment of the present invention, the steps of the first heat treatment and the second heat treatment each comprise: firing or, drying and firing.
According to a preferred embodiment of the present invention, the steps of the first heat treatment and the second heat treatment each comprise a step of drying and firing.
In the present invention, the optional range of the drying conditions is wide, and common drying conditions can be used in the present invention, and for the present invention, the preferable drying conditions include: the temperature is 50-200 ℃ and the time is 1-30 h.
In the present invention, the optional range of the roasting conditions is wide, and all the common roasting conditions can be used in the present invention, and for the present invention, the preferable roasting conditions include: heat-treating for 1-30 hours at 300-700 ℃ in an oxygen-containing atmosphere.
According to a preferred embodiment of the present invention, the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the air to the water vapor is 5-100: 1.
In the invention, the first metal source is a soluble compound containing VB, VIB and VIIB group metals. Common soluble compounds can be used in the present invention and are not described herein.
In the present invention, the second metal source is a soluble compound containing a second metal. Common soluble compounds can be used in the present invention and are not described herein.
In the present invention, the source of acidic molecular sieve components may be selected from, for example, acidic molecular sieve components characterized by an eight-membered, ten-membered or twelve-membered ring pore structure.
In the present invention, the acidic molecular sieve is, for example, at least one selected from the group consisting of ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12 and Y molecular sieves.
In the present invention, the oxide assistant source may be selected from one or more of alumina, silica, magnesia, titania and kaolin, for example.
In the invention, the transalkylation catalyst can be used for transalkylation and has the advantages of high reaction activity, low aromatic hydrocarbon loss and the like.
Before the transalkylation catalyst is used, the transalkylation catalyst is reduced according to the requirement, the reduction step has no special requirement, and the invention is not repeated.
Before the transalkylation catalyst is used, the transalkylation catalyst is reduced according to the requirement, the reduction step has no special requirement, and the invention is not repeated.
In the present invention, the aromatization unit catalyst may be conventionally selected, for example, comprising at least one first component selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, and at least one second component selected from the group consisting of Zn, Ga, Pt, Mo, for example, one or more of Zn/ZSM-5, Mo/ZSM-5, and Mo-Zn/ZSM-5.
In the present invention, the catalyst of the non-aromatic selective cracking unit may be conventionally selected, for example, from at least one acidic molecular sieve having an eight-, ten-or twelve-membered ring structure, such as at least one molecular sieve of ZSM-5, MCM-22, MOR and Beta, and may optionally contain a metal component selected from groups VIB, VIIB and VIII.
According to the process of the present invention, the operating conditions of the aromatization unit in step I) can be selected in a wide range, and according to a preferred embodiment of the present invention, it is preferred that the operating conditions of the aromatization unit in step I) comprise: aromatization unit catalyst selectionOne or more of Zn/ZSM-5, Mo/ZSM-5 and Mo-Zn/ZSM-5, the reaction temperature is 400--1。
According to the process of the present invention, the operating conditions of the transalkylation unit in step II) are widely selectable, and for the present invention, it is preferred that the operating conditions of step II) include: the reaction temperature is 250 ℃ and 500 ℃, the reaction pressure is 1.5-6.5MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 0.5-5h-1。
According to the method, the aromatic hydrocarbon purification unit in the step III) is an aromatic hydrocarbon extraction separation unit or a non-aromatic hydrocarbon selective cracking unit.
According to the method of the present invention, it is preferable that the aromatic hydrocarbon extraction separation unit performs extraction separation using extractive distillation based on a sulfolane solvent.
According to the process of the present invention, it is preferred that the operating conditions of the non-aromatic selective cracking unit comprise: the catalyst contains at least one of molecular sieves of ZSM-5, MCM-22, MOR and Beta, and can selectively contain metal components selected from VIB, VIIB and VIII groups; the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-3.0MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 1-15h-1。
According to the process of the present invention, it is preferred that the operating conditions of the steam cracking unit in step IV) comprise: the temperature of the cracking reaction is 600-1000 ℃.
The invention is further illustrated but is not limited by the following description of the examples.
In the following examples, the catalyst was prepared by a conventional method, unless otherwise specified.
Example 1
The present invention will now be described more fully with reference to fig. 1. The catalytic heavy gasoline with the distillation range of 100-190 ℃ enters an aromatization unit to carry out aromatization reaction (feeding 100 tons/hour) after desulfurization and denitrification, and a product C5 -As steam cracking feedstock, C6 +The components are removed from a transalkylation unit to carry out cracking and transalkylation reactions. C formed by transalkylation unit5 -A de-steam cracking unit; the unreacted C6, C7 and C9+ components are all recycled to the transalkylation unit; c formed by transalkylation unit8The component goes to the aromatics purification unit (non-aromatics cracking unit) and further cracks the non-aromatic components. C produced by non-aromatic cracking unit5 -And (3) removing light non-aromatic hydrocarbon from a steam cracking unit to obtain a carbon octaarene product with the purity of 99.8 percent.
Operating conditions of an aromatization unit:
the catalyst is a ZSM-5 molecular sieve catalyst loaded with 3 percent (by weight) of Zn, the reaction temperature is 520 ℃, the reaction pressure is 0.5MPa, and the feeding weight space velocity is 1.5;
transalkylation unit operating conditions:
the catalyst is a mordenite catalyst loaded with 2 percent (weight) of Mo (the Mo is loaded on the mordenite by a one-step impregnation method), the reaction temperature is 360 ℃, the reaction pressure is 3.0MPa, the feed weight space velocity is 3.0, and the hydrogen-hydrocarbon molar ratio is 5.0;
operating conditions of a non-aromatic cracking unit (aromatic purification unit):
the catalyst is a ZSM-5 molecular sieve catalyst loaded with 0.1 percent (weight) of Pt, the reaction temperature is 450 ℃, the reaction pressure is 2.5MPa, and the feeding weight space velocity is 6.0;
the raw material composition is shown in table 1, the unit reaction conditions are shown in table 2, and the integrated plant product yield is shown in table 3.
Example 2
The invention will now be described with reference to fig. 2. The catalytic cracking gasoline (full-range catalytic gasoline) with the distillation range of 60-200 ℃ enters an aromatization unit to carry out aromatization reaction (the feeding amount is 100 tons/hour) after desulfurization and denitrification, and the product C5 -As steam cracking feedstock, C6 +The components are removed from a transalkylation unit to carry out cracking and transalkylation reactions. C formed by transalkylation unit5 -Removing steam cracking unit, unreacted C6、 C7And C9+ component(s) being recycled partially or wholly to the transalkylation unit, C being formed in the transalkylation unit8The component is removed from a non-aromatic hydrocarbon cracking unit (aromatic hydrocarbon purification unit) to further crack non-aromatic components, and the generated C5Light non-aromatic steam cracking unitAnd the carbon octaarene product with the purity of 99.6 percent is obtained.
Operating conditions of an aromatization unit:
the catalyst is ZSM-5 molecular sieve catalyst loaded with 2 wt% Zn, the reaction temperature is 480 ℃, the reaction pressure is 0.5MPa, and the feeding weight space velocity is 1.0;
transalkylation unit operating conditions:
the catalyst is a mordenite catalyst loaded with 1% (weight) of Ni and 4% (weight) of Mo (Ni and Mo are loaded on mordenite by a one-step impregnation method), the reaction temperature is 370 ℃, the reaction pressure is 3.0MPa, the feed weight space velocity is 3.0, and the hydrogen-hydrocarbon molar ratio is 4.0;
operating conditions of a non-aromatic cracking unit (aromatic purification unit): the catalyst is ZSM-5 molecular sieve catalyst loaded with 5 wt% of Mo, the reaction temperature is 430 ℃, the reaction pressure is 2.5MPa, and the feeding weight space velocity is 4.0;
the raw material composition is shown in table 1, the unit reaction conditions are shown in table 2, and the integrated plant product yield is shown in table 3.
Example 3
The catalytic cracking full-fraction gasoline (catalytic gasoline) with the distillation range of 70-200 ℃ enters an aromatization unit to carry out aromatization reaction (the feeding amount is 100 tons/hour) after desulfurization and denitrification, and a product C5 -As steam cracking feedstock, C6 +The components are removed from a transalkylation unit to carry out cracking and transalkylation reactions. C formed by transalkylation unit5 -And (3) a steam cracking removal unit, wherein unreacted C6, C7 and C9+ components are partially or completely recycled to the transalkylation unit, the C8 component generated by the transalkylation unit is removed to an aromatic hydrocarbon extraction unit (aromatic hydrocarbon purification unit), non-aromatic hydrocarbon is extracted and removed to the steam cracking unit, and high-purity C8 aromatic hydrocarbon is extracted as a product.
Operating conditions of an aromatization unit:
the catalyst is ZSM-5 molecular sieve catalyst loaded with 2 wt% of Zn, the reaction temperature is 550 ℃, the reaction pressure is 1.0MPa, and the feed weight space velocity is 1.0h-1；
Transalkylation unit operating conditions: the catalyst is a mordenite catalyst loaded with 0.1 percent (weight) of Pt (the Pt is loaded on the mordenite by a Pt one-step impregnation method), the reaction temperature is 370 ℃, the reaction pressure is 3.0MPa, the feeding weight space velocity is 2.0, and the hydrogen-hydrocarbon molar ratio is 3.0.
The raw material composition is shown in table 1, the unit reaction conditions are shown in table 2, and the integrated plant product yield is shown in table 3.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Raw materials | Catalytic cracking heavy gasoline | Catalytic cracking gasoline | Catalytic cracking gasoline |
| Sulfur content, ppm-wt | 5 | 3 | 6 |
| Nitrogen content ppm-wt | 2 | 1 | 3 |
| Aromatic hydrocarbons, wt.% | 38 | 21 | 17 |
| Olefin, wt.% | 25 | 36 | 41 |
| Alkane, wt.% | 37 | 43 | 42 |
| Distillation range, deg.C | 100-190 | 60-200 | 70-200 |
TABLE 2
| Example 1 | Example 2 | Example 3 | |
| Reaction unit | Parameter(s) | Parameter(s) | Parameter(s) |
| Aromatization unit | |||
| Temperature, C | 520 | 480 | 550 |
| Pressure, MPa | 0.5 | 0.5 | 1.0 |
| Mass space velocity h-1 | 1.5 | 1.0 | 1.0 |
| Transalkylation unit | |||
| Temperature, C | 360 | 370 | 370 |
| Pressure, MPa | 3.0 | 3.0 | 3.0 |
| Mass space velocity h-1 | 3.0 | 3.0 | 2.0 |
| Hydrogen to hydrocarbon molar ratio | 5 | 4 | 3.0 |
| Non-aromatic cracking unit | |||
| Temperature, C | 450 | 430 | |
| Pressure, MPa | 2.5 | 2.5 | |
| Mass space velocity h-1 | 6.0 | 4.0 | |
| Hydrogen to hydrocarbon molar ratio | 4 | 4 | |
| Steam cracking unit | |||
| Temperature, C | 850 | 850 | 850 |
TABLE 3
Preparation of example 1
Taking 18 g of mordenite and 2 g of ZSM-5 molecular sieve, uniformly mixing, then soaking in a certain ammonium molybdate solution to prepare modified molecular sieve powder, and roasting the modified molecular sieve for 3 hours at the temperature of 400 ℃ in the air atmosphere after the modified molecular sieve is subjected to spray drying at the temperature of 150 ℃. 7.7 g of alumina is taken and dipped into a certain amount of strontium nitrate with the same volume to prepare modified alumina, and the modified alumina is sprayed and dried at 150 ℃ and roasted for 3 hours at 400 ℃ in air atmosphere. Kneading the modified molecular sieve and the modified alumina for molding, and roasting at 550 ℃ for 2 hours to obtain the catalyst A with the molybdenum content of 1 percent (wt) and the strontium content of 1.0 percent (wt).
Preparation of example 2
15 g of mordenite molecular sieve and 5 g of ZSM-5 molecular sieve are mixed and then dipped into a certain ammonium molybdate solution to prepare modified molecular sieve powder, and the modified molecular sieve is dried for 10 hours at 120 ℃ and then roasted for 3 hours at 450 ℃ in air atmosphere. 7.7 g of alumina is taken and dipped into a certain amount of bismuth nitrate with the same volume to prepare modified alumina, the modified alumina is dried for 10 hours at 120 ℃, and is roasted for 3 hours at 400 ℃ in air atmosphere. Kneading the modified molecular sieve and the modified alumina for molding, and roasting at 500 ℃ for 6 hours to prepare the catalyst B with the molybdenum content of 3 percent (wt) and the bismuth content of 5 percent (wt).
Preparation of example 3
15 g of mordenite molecular sieve and 5 g of ZSM-5 molecular sieve are uniformly mixed and dipped into a certain ammonium molybdate solution in equal volume to prepare modified molecular sieve powder, and the modified molecular sieve is dried at 120 ℃ for 10 hours and then roasted at 500 ℃ for 3 hours in air atmosphere. 7.7 g of alumina is taken and dipped into certain cerium nitrate with equal volume to prepare modified alumina, and the modified alumina is dried for 10 hours at 120 ℃ and then roasted for 3 hours at 400 ℃ in air atmosphere. Kneading the modified molecular sieve and the modified alumina for molding, and roasting at 550 ℃ for 2 hours to obtain the catalyst C with the molybdenum content of 13% (wt) and the cerium content of 8.0% (wt).
Preparation of example 4
15 g of mordenite molecular sieve and 5 g of ZSM-5 molecular sieve are mixed and then dipped into a certain ammonium molybdate solution to prepare modified molecular sieve powder, the modified molecular sieve is rapidly spray-dried at 160 ℃, and then is roasted for 3 hours at 500 ℃. 7.7 g of alumina is taken to be dipped in a certain bismuth nitrate in equal volume to prepare modified alumina, the modified alumina is quickly sprayed and dried at 160 ℃, and then is roasted for 3 hours at 500 ℃ in air atmosphere. Kneading the modified molecular sieve and the modified alumina for molding, and roasting at 500 ℃ for 6 hours to prepare the catalyst D with the molybdenum content of 3 percent (wt) and the bismuth content of 5 percent (wt).
Preparation of example 5
15 g of mordenite molecular sieve and 5 g of ZSM-5 molecular sieve are mixed and then dipped into a certain ammonium molybdate solution to prepare modified molecular sieve powder, and the modified molecular sieve is roasted for 3 hours at 500 ℃. 7.7 g of alumina is taken and dipped into a certain amount of bismuth nitrate with the same volume to prepare modified alumina, and the modified alumina is dried at 160 ℃ and then roasted for 3 hours with air at 500 ℃. Kneading the modified molecular sieve and the modified alumina for molding, and roasting at 550 ℃ for 3 hours to prepare the catalyst E with the molybdenum content of 3 percent (wt) and the bismuth content of 5 percent (wt).
Preparation of example 6
Taking 15 g of Beta molecular sieve and 5 g of ZSM-5 molecular sieve, uniformly mixing, soaking a certain amount of high ammonium rhenate solution to prepare modified molecular sieve powder, drying the modified molecular sieve at 120 ℃ for 10 hours, and roasting at 500 ℃ for 3 hours in air atmosphere. 7.7 g of alumina is taken and dipped into a certain amount of germanium chloride with the same volume to prepare modified alumina, and the modified alumina is dried at 120 ℃ for 10 hours and roasted at 500 ℃ for 3 hours in air atmosphere. The modified molecular sieve and the modified alumina are kneaded and molded, and roasted for 2 hours at 550 ℃ to obtain the catalyst F with the rhenium content of 1 percent (wt) and the germanium content of 3.0 percent (wt).
Preparation of example 7
Uniformly mixing 15 g of ZSM-12 molecular sieve and 5 g of ZSM-5 molecular sieve, soaking a certain ammonium molybdate solution in an equal volume to prepare modified molecular sieve powder, drying the modified molecular sieve at 120 ℃ for 10 hours, and roasting the modified molecular sieve at 400 ℃ for 3 hours in an air atmosphere. 4 g of alumina and 3.5 g of magnesia are uniformly mixed and dipped with a certain amount of zirconium chloride in equal volume to prepare a modified oxide, the modified oxide is dried for 10 hours at 120 ℃, and then is roasted for 3 hours at 400 ℃ in an air atmosphere. Kneading the modified molecular sieve and the modified oxide for molding, and roasting at 500 ℃ for 4 hours to obtain the catalyst G with the molybdenum content of 8 percent (wt) and the zirconium content of 5.0 percent (wt).
Preparation of example 8
The preparation was carried out according to the method of preparation example 1, except that 18 g of mordenite molecular sieve and 2 g of ZSM-5 molecular sieve were mixed uniformly and immersed in a certain volume of ammonium molybdate and ammonium tungstate solution, and the other conditions were the same, to obtain catalyst I.
Preparation of example 9
The preparation was carried out according to the method of preparation example 1, except that 18 g of mordenite molecular sieve and 2 g of ZSM-5 molecular sieve were mixed uniformly and impregnated with a solution of ammonium molybdate, ammonium tungstate and ammonium perrhenate in equal volume, and the other conditions were the same, to obtain catalyst J.
Preparation of example 10
The preparation method is as described in preparation example 1, except that 18 g of mordenite molecular sieve and 2 g of ZSM-5 molecular sieve are uniformly mixed and dipped into a certain ammonium molybdate solution in equal volume to prepare modified molecular sieve powder, the modified molecular sieve is dried at 120 ℃ for 10 hours and then calcined at 400 ℃ for 3 hours in a mixed atmosphere of air and water vapor (the volume ratio of air to water vapor is 20: 1), and the preparation, reduction and reaction conditions of the rest catalysts are the same to obtain the catalyst M with the molybdenum content of 1% (wt) and the strontium content of 1.0% (wt).
Preparation of example 11
The preparation method is as described in preparation example 1, except that 18 g of mordenite molecular sieve and 2 g of ZSM-5 molecular sieve are uniformly mixed and immersed in a certain ammonium molybdate solution in equal volume to prepare modified molecular sieve powder with a molybdenum content of 1% (wt), the modified molecular sieve is dried at 120 ℃ for 10 hours and then calcined in a mixed atmosphere of air and water vapor (the volume ratio of air to water vapor is 5: 1) at 400 ℃ for 3 hours, and the preparation, reduction and reaction conditions of the rest catalysts are the same to obtain catalyst N with a molybdenum content of 1% (wt) and a strontium content of 1.0% (wt).
Preparation of example 12
The preparation method is as described in preparation example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve are uniformly mixed and dipped in a certain ammonium molybdate solution in equal volume to prepare modified molecular sieve powder, the modified molecular sieve is dried at 120 ℃, 7.7 g of alumina is dipped in a certain strontium nitrate in equal volume to prepare modified alumina, and the modified alumina is spray-dried at 150 ℃. Kneading and molding the modified molecular sieve and the modified alumina, roasting at 550 ℃ for 2 hours to obtain a catalyst A, wherein the preparation, reduction and reaction conditions of the rest catalysts are the same, and thus the catalyst O with the molybdenum content of 1% (wt) and the strontium content of 1.0% (wt) is obtained.
Examples 4 to 15
Catalysts A to O were placed in a reactor and reduced with hydrogen at 450 ℃ for 3 hours before use, and then gasoline was treated in the same manner as in example 1 except that the transalkylation catalyst of example 1 was replaced with the catalysts A to O of this preparative example and the remaining operating conditions were unchanged, and the results are shown in Table 4.
TABLE 4
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (11)
1. A process for producing aromatics and olefins, the process comprising:
I) the mixed hydrocarbon raw material containing aromatic hydrocarbon enters an aromatization unit to contact and react with a catalyst of the aromatization unit, and reaction products are separated to obtain C5 -Component C6 +Preparing components;
II) C in step I)6 +The components enter a transalkylation unit to contact and react with a transalkylation catalyst,
separating the reaction product to obtain C5 -Component C8Component (A) comprising C6 +The remaining components of (a);
III) step II) C8The components enter an aromatic hydrocarbon purification unit to separate high-purity C8 aromatic hydrocarbon and C5 -Component (A) and (B) comprises6 +The remaining components of (a);
IV) step I) C5 -Component(s) and/or C in step II)5 -Component(s) and/or C in step III)5 -The components enter a steam cracking unit for steam cracking;
v) step II) comprises C6 +And/or step III) comprises C6 +And the remaining components are returned, in whole or in part, to the transalkylation unit.
2. The process of claim 1, wherein the transalkylation catalyst in step II) comprises an acidic molecular sieve component, an oxidation promoter, a first metal and/or a first metal oxide, wherein the first metal is selected from one or more of groups VB, VIB and VIIB, and a second metal and/or a second metal oxide, wherein the second metal is a different metal component than the first metal; the first metal and/or first metal oxide is/are immobilized on the acidic molecular sieve component.
3. The method of claim 2, wherein,
the preparation steps of the transalkylation catalyst comprise: immobilizing a first metal and/or a first metal oxide on the acidic molecular sieve, and immobilizing a second metal and/or a second metal oxide on an oxide auxiliary agent; then kneading and molding the two.
4. A process according to claim 2 or claim 3, wherein the acidic molecular sieve component is present in an amount of from 50 to 80 wt%, the oxide promoter is present in an amount of from 10 to 30 wt%, the first metal and/or first metal oxide is present in an amount of from 0.05 to 18 wt% and the second metal and/or second metal oxide is present in an amount of from 0.05 to 18 wt%, based on 100 wt% of catalyst.
5. The method according to any one of claims 2 to 4,
the second metal is selected from one or more of group IA, IIA, IIIA, IVA, VA and lanthanide metals, preferably one or more of Sr, Bi, Ce, Zr and Ge.
6. The method of any one of claims 2-5,
the first metal is selected from one or more of Mo, Re and W, preferably the first metal is at least two of Mo, Re and W, and the mixing weight ratio of the Mo, Re and W is 0.1-10: 1; more preferably a combination of the three, and the weight ratio of Mo, Re and W is 1: 0.1-0.4: 0.1-0.6.
7. The method of any one of claims 2-6,
the acidic molecular sieve component is selected from acidic molecular sieve components having eight-membered, ten-membered or twelve-membered ring pore structure characteristics; preferably at least one selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12 and Y molecular sieves.
8. The method of any one of claims 2-7,
the oxide auxiliary agent is selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide and kaolin.
9. The process of any of claims 2-8, wherein the transalkylation catalyst is prepared by a process comprising:
(1) impregnating a first metal source solution with the acidic molecular sieve component source, and carrying out first heat treatment to obtain a first solid;
dipping a second metal source solution into an oxide auxiliary agent source, and performing second heat treatment to obtain a second solid;
(2) kneading the first solid and the second solid, and forming.
10. The method of claim 9, wherein,
in the step (1), the steps of the first heat treatment and the second heat treatment each include: calcination or, alternatively, drying and calcination,
wherein the drying conditions include: the temperature is 50-200 ℃, and the time is 1-30 h;
wherein, the roasting conditions comprise: heat-treating for 1-30 hours at 300-700 ℃ in an oxygen-containing atmosphere; preferably, the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the air to the water vapor is 5-100: 1.
11. The method of any one of claims 1-10,
the boiling range of the mixed hydrocarbon raw material containing the aromatic hydrocarbon in the step I) is 50-250 ℃, and the boiling range of the mixed hydrocarbon raw material containing the aromatic hydrocarbon is preferably 60-210 ℃; and/or
In the step I), the aromatic hydrocarbon content of the mixed hydrocarbon raw material containing the aromatic hydrocarbon is 10-100 percent by weight, and the aromatic hydrocarbon content is preferably 20-80 percent by weight; and/or
In the step I), the mixed hydrocarbon raw material containing the aromatic hydrocarbon is selected from catalytic cracking gasoline, hydrocracking gasoline, ethylene cracking gasoline, catalytic reforming gasoline, straight-run gasoline, LPG or any mixture thereof.
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