CN109395716A - Increase production light aromatics catalyst - Google Patents
Increase production light aromatics catalyst Download PDFInfo
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- CN109395716A CN109395716A CN201710709603.2A CN201710709603A CN109395716A CN 109395716 A CN109395716 A CN 109395716A CN 201710709603 A CN201710709603 A CN 201710709603A CN 109395716 A CN109395716 A CN 109395716A
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- Prior art keywords
- catalyst
- compound
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- light aromatics
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims description 81
- 239000001257 hydrogen Substances 0.000 claims description 81
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 67
- 239000002184 metal Substances 0.000 claims description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- -1 alcohol compound Chemical class 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 28
- 229910052726 zirconium Inorganic materials 0.000 claims description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 229910052758 niobium Inorganic materials 0.000 claims description 20
- 239000010955 niobium Substances 0.000 claims description 20
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 238000000576 coating method Methods 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
- 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
- 150000002822 niobium compounds Chemical class 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 117
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 102
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 54
- 230000009257 reactivity Effects 0.000 description 50
- 238000005470 impregnation Methods 0.000 description 47
- 239000000243 solution Substances 0.000 description 44
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 239000000463 material Substances 0.000 description 27
- 239000002994 raw material Substances 0.000 description 26
- 238000011835 investigation Methods 0.000 description 25
- 239000000969 carrier Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 13
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012913 prioritisation Methods 0.000 description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 2
- 229910001630 radium chloride Inorganic materials 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RZDSZOMCGARBBI-UHFFFAOYSA-N nitric acid vanadium Chemical compound [V].[N+](=O)(O)[O-] RZDSZOMCGARBBI-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/397—
-
- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The present invention relates to a kind of volume increase light aromatics catalyst, mainly solve to exist in the prior art that condensed-nuclei aromatics hydrogenation selectivity is not high, the high problem of mononuclear aromatics loss late.The present invention passes through a kind of condensed-nuclei aromatics selective hydrocatalyst, it include: containing nonacid or faintly acid porous carrier, and at least two metallic elements or compound selected from VIII, IV B, V B of load thereon, the metallic element or compound are in the technical solution of nuclear shell distribution on the surface of the carrier, condensed-nuclei aromatics hydrogenation selectivity is significantly improved, mononuclear aromatics loss is reduced.
Description
Technical field
The present invention relates to a kind of volume increase light aromatics catalyst and preparation method thereof.
Background technique
Condensed-nuclei aromatics refers to bicyclic and multiring structure aromatic component, be largely present in catalytic cracking, ethylene bottom oil and
PX production process, it is most of by as diesel oil blending component if catalytic cracking light cycle oil annual output is more than 10,000,000 tons.Closely
With the continuous increase of China's PX demand over year, the situation that supply falls short of demand is presented in PX.Realize Aromatic Hydrocarbon United Plant enlargement and
Raw material diversification is to solve one of the key factor of present problems.Therefore, make full use of Aromatic Hydrocarbon United Plant by-product condensed-nuclei aromatics,
The condensed-nuclei aromatics of research and utilization oil refining apparatus by-product is of great significance to produce light aromatics.From the point of view of reaction process, realize
Condensed-nuclei aromatics to mononuclear aromatics conversion most critical the step of first is that realize condensed-nuclei aromatics selective hydrogenation, by polycyclic aromatic hydrocarbon
Partial hydrogenation generates mononuclear aromatics component.It is coexisted in system in monocycle and polycyclic aromatic hydrocarbon, realizes that arenes selectivity adds hydrogen to be to improve
The significant process of mononuclear aromatics yield.The mononuclear aromatics such as benzene, toluene are controlled while producing mononuclear aromatics adds hydrogen saturation, gold
Belong to the metals such as platinum, palladium and base metal molybdenum, nickel have been reported for polycyclic aromatic hydrocarbon plus hydrogen saturation.
CN104117386A discloses a kind of condensed-nuclei aromatics and adds hydrogen ring opening catalyst, and catalyst is containing 5%-100%'s
Beta molecular sieve component, and the noble metal for selecting Pt, Ir, Pd of the 0.1%-3% of load thereon.
CN102688770A discloses a kind of aromatic hydrocarbon hydrogenation catalyst, is to form with mesoporous zeolite and noble metal, improves
The hydrogenation aromatics-removing activity and sulfur resistance of catalyst.
CN103301874B discloses the method and carbon monoxide-olefin polymeric of a kind of polycyclic aromatic hydrocarbon selective hydrogenation open loop, including
Acidic molecular sieve loads VIII family metal oxide and catalyst containing Mo, and catalyst containing Mo is Mo and the bimetallic of transition metal composition
Sulfide significantly improves the yield of selective opening product using combination catalyst and water additive.
CN103666553 discloses a kind of method of hydro-conversion polycyclic aromatic hydrocarbon, and polycyclic aromatic hydrocarbon is first in hydroconversion reaction zone
It is at least partially saturated, 40% or more polycyclic aromatic hydrocarbon conversion ratio of acquisition, mononuclear aromatics yield 4-80%,；Pass through hydrocracking again
Reaction zone reaction, obtains 85% or more polycyclic aromatic hydrocarbon conversion ratio, mononuclear aromatics yield advantage 4-30%, to reduce polycyclic aromatic hydrocarbon
Convert hydrogen consumption.
Above patent document is not directed to that monocycle, condensed-nuclei aromatics coexists under system, realizes that condensed-nuclei aromatics is highly selective
Partial hydrogenation technology.
Summary of the invention
The technical problem to be solved by the present invention is to the prior art, that there are condensed-nuclei aromatics hydrogenation selectivities is low, mononuclear aromatics is received
The low problem of rate, provides a kind of new condensed-nuclei aromatics selective hydrocatalyst, the catalyst for handle containing mononuclear aromatics with
When condensed-nuclei aromatics material, have condensed-nuclei aromatics selective hydrogenation rate high, mononuclear aromatics loses small advantage.
In order to solve the above technical problems, the present invention is as follows using technical solution: a kind of volume increase light aromatics catalyst
It include: and load at least two VIII, IV B of selection thereon, V B containing nonacid or faintly acid porous carrier
Metallic element or compound；The metallic element or compound are in nuclear shell distribution on the surface of the carrier.
In above-mentioned technical proposal, nonacid or faintly acid porous carrier is selected from aluminium oxide, amorphous silica-alumina, kaolin, silicon
At least one of aluminate.The metal in Pt, Pd, Ir, Rh, Ti, V, Zr, Nb at least two.
The nuclear phase layer metal is selected from least one of metal and its compound of Ti, V, Zr, Nb.The shell phase layer gold
Belong to selected from least one of Pt, Pd, Ir, Rh metal and its compound.
In more optimized scheme, nuclear phase layer metal includes the mixture of Zr and Nb simultaneously, wherein the weight of the compound of Zr and Nb
Amount is than being (0.1~10): 1；The mixture of Zr and Nb has synergistic effect in terms of the selective hydrogenation for improving fused ring compound.
In more optimized scheme, shell phase layer metal includes the mixture of Pt and Pd simultaneously, wherein the weight of the compound of Pt and Pd
Amount is than being (0.1~5): 1；Pt and Pd mixture in terms of the selective hydrogenation activity for improving fused ring compound there is collaboration to make
With.
The condensed-nuclei aromatics selective hydrocatalyst, based on parts by weight, nuclear phase layer tenor are catalyst
0.01-20 part of total weight, prioritization scheme are 0.1-10 parts；Shell phase layer tenor is 0.01-10 part of total catalyst weight,
Prioritization scheme is 0.02-5 parts.
To solve above-mentioned technical problem two, the present invention is as follows using technical solution: a kind of volume increase light aromatics catalyst
Preparation method, comprising:
A) salt of containing nuclear phase layer metal is dissolved in water or non-aqueous solution, then is existed by the method for precipitating, physics bonding, dipping
One layer of metallic compound of supported on carriers roasts in 400-600 DEG C after dry, the catalyst I with nuclear phase layer structure is made.
B) salt containing shell phase layer metal is dissolved in water or non-aqueous solution, then negative by dipping, precipitating or coating process
It is loaded on catalyst I, is roasted after dry in 400-600 DEG C, volume increase light aromatics catalyst is made；
Wherein, a) metal salt in step is selected from titanium-containing compound, vanadium-containing compound, zirconium-containing compound, contains niobium compound
At least one of, the non-aqueous solution is selected from one kind of alcohol compound, ketone compounds, petroleum ether；B) gold in step
Belong to salt to be selected from compound containing platinum, containing palladium compound, contain at least one of iridic compound, rhodium-containing compound, the non-aqueous solution
Selected from one of alcohol compound, ketone compounds, petroleum ether.
The catalyst is 100-500 DEG C, reaction pressure 0.5-8MPa in reaction temperature, and hydrogen hydrocarbon molar ratio is 1-10,
Feed weight air speed is reacted under the conditions of being 0.5-20.
In the present invention, based on the interaction between nuclear shell carried metal, the electronic characteristic of shell metallic can be effectively adjusted,
To which modulation shell metallic is to aromatics absorption intensity, the selective hydrogenation activity to condensed-nuclei aromatics is improved.The catalyst treatment is thick
When cyclophane hydrocarbon material, have condensed-nuclei aromatics selective hydrogenation rate high, mononuclear aromatics loses small advantage.
Below by the description to embodiment, further illustrates but does not limit the present invention:
Specific embodiment
[embodiment 1]
Take 20 grams of alumina balls carriers, the certain chlorination zirconium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A1 that zirconium content is 3% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A1 incipient impregnation
Platinum content is the nucleocapsid metal layer catalyst B1 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B1 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 370 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.React item
Part are as follows: total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials
For toluene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.R2/R1 indicates naphthalene weight hydrogenation rate and toluene by weight in table
The ratio between hydrogenation rate has reacted catalyst to the hydrogenation selectivity of condensed-nuclei aromatics.
[embodiment 2]
Take 20 grams of alumina balls carriers, the certain chlorination zirconium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A2 that zirconium content is 6% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A2 incipient impregnation
Platinum content is the nucleocapsid metal layer catalyst B2 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B2 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 370 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 3]
Take 20 grams of alumina balls carriers, the certain chlorination zirconium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A3 that zirconium content is 3% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A3 incipient impregnation
Platinum content is the nucleocapsid metal layer catalyst B3 of 0.5% (wt).
5 grams of nucleocapsid metal layer catalyst B3 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 4]
Take 20 grams of alumina balls carriers, the certain chlorination zirconium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A4 that zirconium content is 3% (wt) is made and obtains the certain chlorine palladium acid solution of catalyst A4 incipient impregnation
Palladium content is the nucleocapsid metal layer catalyst B4 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B4 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 5]
Take 20 grams of alumina balls carriers, the certain chlorination zirconium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A5 that zirconium content is 3% (wt) is made and obtains the certain Chloroiridic Acid solution of catalyst A5 incipient impregnation
Iridium content is the nucleocapsid metal layer catalyst B5 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B5 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 6]
Take 20 grams of alumina balls carriers, the certain nitric acid vanadium solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A6 that content of vanadium is 3% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A6 incipient impregnation
Pt content is the nucleocapsid metal layer catalyst B6 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B6 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 7]
Take 20 grams of alumina balls carriers, the certain titanium trichloride solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings
It burns 4 hours, the modified catalyst A7 that Ti content is 3% (wt) is made, by the certain platinum acid chloride solution of catalyst A7 incipient impregnation,
Obtain the nucleocapsid metal layer catalyst B7 that platinum content is 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B7 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 8]
Take 20 grams of alumina balls carriers, the certain niobium oxalate solution of incipient impregnation, 120 DEG C drying 4 hours, 550 DEG C of roastings 4
Hour, the modified catalyst A8 that content of niobium is 3% (wt) is made and obtains the certain platinum acid chloride solution of catalyst A8 incipient impregnation
Platinum content is the nucleocapsid metal layer catalyst B8 of 0.3% (wt).
5 grams of nucleocapsid metal layer catalyst B8 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 9]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and sodium vanadate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A9 that zirconium content is 1% (wt), content of vanadium is 2% (wt) are made, by catalyst A9 etc.
The certain chloroplatinic acid of volume impregnation and palladium chloride solution obtain the nucleocapsid metal layer that platinum content is 0.1% (wt), palladium content is 0.2%
Catalyst B9.
5 grams of nucleocapsid metal layer catalyst B9 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to
It 350 DEG C, is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total
Weight space velocity is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene:
Naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 10]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and titanium chloride solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A10 that zirconium content is 1% (wt), Ti content is 2% (wt) are made, by catalyst A10
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B10.
5 grams of nucleocapsid metal layer catalyst B10 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 11]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A11 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A11
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B11.
5 grams of nucleocapsid metal layer catalyst B11 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 12]
Take 20 grams of alumina balls carriers, the certain sodium vanadate of incipient impregnation and titanium trichloride solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A12 that content of vanadium is 1% (wt), Ti content is 2% (wt) are made, by catalyst A12
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B12.
5 grams of nucleocapsid metal layer catalyst B12 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 13]
Take 20 grams of alumina balls carriers, the certain sodium vanadate of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A13 that content of vanadium is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A13
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B13.
5 grams of nucleocapsid metal layer catalyst B13 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 14]
Take 20 grams of alumina balls carriers, the certain titanium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A14 that Ti content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A14
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B14.
5 grams of nucleocapsid metal layer catalyst B14 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 15]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A15 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A15
The certain chloroplatinic acid of incipient impregnation and rhodium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), rhodium content is 0.2%
Layer catalyst B135.
5 grams of nucleocapsid metal layer catalyst B15 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 16]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A16 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A16
The certain radium chloride of incipient impregnation and chlorine palladium acid solution obtain the nucleocapsid metal that rhodium content is 0.1% (wt), palladium content is 0.2%
Layer catalyst B16.
5 grams of nucleocapsid metal layer catalyst B16 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 17]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A17 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A17
The certain radium chloride of incipient impregnation and chloro-iridic acid and solution obtain the nucleocapsid gold that rhodium content is 0.1% (wt), iridium content is 0.2%
Belong to layer catalyst B17.
5 grams of nucleocapsid metal layer catalyst B17 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 18]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A18 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A18
The certain chloroplatinic acid of incipient impregnation and iridium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), iridium content is 0.2%
Layer catalyst B18.
5 grams of nucleocapsid metal layer catalyst B18 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 19]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A19 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A19
The certain chloroplatinic acid of incipient impregnation and palladium chloride solution obtain the nucleocapsid gold that platinum content is 0.03% (wt), palladium content is 0.27%
Belong to layer catalyst B19.
5 grams of nucleocapsid metal layer catalyst B19 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 20]
Take 20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution, 120 DEG C drying 4 hours,
550 DEG C roast 4 hours, the modified catalyst A20 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst A20
The certain chloroplatinic acid of incipient impregnation and rhodium chloride solution obtain the nucleocapsid metal that platinum content is 0.1% (wt), rhodium content is 0.2%
Layer catalyst B20.
5 grams of nucleocapsid metal layer catalyst B20 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 21]
20 grams of balloon borne bodies of amorphous silicon aluminium, the certain zirconium chloride of incipient impregnation and niobium oxalate solution are taken, 120 DEG C of dryings 4 are small
When, 550 DEG C roast 4 hours, the modified catalyst A21 that zirconium content is 1% (wt), content of niobium is 2% (wt) are made, by catalyst
The certain chloroplatinic acid of A21 incipient impregnation and palladium chloride solution obtain the nucleocapsid gold that platinum content is 0.1% (wt), palladium content is 0.2%
Belong to layer catalyst B21.
5 grams of nucleocapsid metal layer catalyst B21 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[embodiment 22]
Take the shaping carrier carrier of 20 grams of Y molecular sieves (Si/Al=30) and aluminium oxide, the certain zirconium chloride of incipient impregnation and
Niobium oxalate solution, 120 DEG C drying 4 hours, 550 DEG C roast 4 hours, be made zirconium content be 1% (wt), content of niobium is 2% (wt)
Modified catalyst A22, by the certain chloroplatinic acid of catalyst A22 incipient impregnation and palladium chloride solution, obtaining platinum content is 0.1%
(wt), the nucleocapsid metal layer catalyst B22 that palladium content is 0.2%.
5 grams of nucleocapsid metal layer catalyst B22 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then cools down
To 350 DEG C, it is passed through hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows:
Total weight air speed is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are first
Benzene: naphthalene=40:60 (weight), reactivity worth is as shown in table 1.
[comparative example 1]
20 grams of alumina balls carriers are taken, the certain platinum acid chloride solution of incipient impregnation obtains the catalysis that platinum content is 0.3% (wt)
Agent B23.
5 grams of catalyst B23 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[comparative example 2]
20 grams of alumina balls carriers, the certain chloroplatinic acid of incipient impregnation and chlorine palladium acid solution are taken, obtaining platinum content is 0.1%
(wt), the catalyst B24 of palladium content 0.2%.
5 grams of catalyst B24 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
[comparative example 3]
20 grams of alumina balls carriers, the certain zirconium chloride of incipient impregnation and niobium oxalate solution are taken, obtaining zirconium content is 1%
(wt), the catalyst B25 that content of niobium is 2%.
5 grams of catalyst B25 are placed in reactor, logical hydrogen restores 3 hours at 450 DEG C, then is cooled to 350 DEG C, leads to
Enter hydrogen and containing toluene and naphthalene material contacts with catalyst and carries out reactivity investigation.Reaction condition are as follows: total weight air speed
It is 10 hours-1, 370 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 4.0.Reaction raw materials are toluene: naphthalene=40:60
(weight), reactivity worth is as shown in table 1.
Table 1
Claims (9)
1. a kind of volume increase light aromatics catalyst, which is characterized in that catalyst includes:
A) contain nonacid or faintly acid porous carrier, and load thereon
B) at least two metallic element or compound selected from VIII, IV B, V B
Wherein, the metallic element or compound are in nuclear shell distribution on the surface of the carrier.
2. volume increase light aromatics catalyst according to claim 1, it is characterised in that nonacid or faintly acid porous carrier
Selected from least one of aluminium oxide, amorphous silica-alumina, kaolin, alumino-silicate.
3. volume increase light aromatics catalyst according to claim 1, it is characterised in that the metal be selected from Pt, Pd, Ir,
At least two in Rh, Ti, V, Zr, Nb.
4. volume increase light aromatics catalyst according to claim 1, it is characterised in that the nuclear phase layer metal be selected from Ti, V,
At least one of metal and its compound of Zr, Nb.
5. volume increase light aromatics catalyst according to claim 1, it is characterised in that the shell phase layer metal be selected from Pt,
At least one of Pd, Ir, Rh metal and its compound.
6. volume increase light aromatics catalyst according to claim 1, which is characterized in that based on parts by weight, nuclear phase layer gold
Belong to 0.01-20 part that content is overall catalyst weight.
7. volume increase light aromatics catalyst according to claim 1, which is characterized in that based on parts by weight, shell phase layer gold
Belong to 0.01-10 part that content is overall catalyst weight.
8. a kind of preparation method using any one volume increase light aromatics catalyst described in claim 1~7, feature exist
In, comprising:
A) salt of containing nuclear phase layer metal is dissolved in water or non-aqueous solution, then by precipitating, physics bonding, the method impregnated in carrier
One layer of metallic compound of upper load roasts in 400-600 DEG C after dry, the catalyst I with nuclear phase layer structure is made.
B) salt containing shell phase layer metal is dissolved in water or non-aqueous solution, then negative by dipping, absorption, precipitating or coating process
It is loaded on the catalyst I with nuclear phase layer structure, is roasted after dry in 400-600 DEG C, volume increase light aromatics catalyst is made；
Wherein, a) metal salt in step selected from titanium-containing compound, vanadium-containing compound, zirconium-containing compound, containing in niobium compound
At least one, the non-aqueous solution are selected from one of alcohol compound, ketone compounds, petroleum ether；B) metal in step
Salt is selected from compound containing platinum, containing palladium compound, contains at least one of iridic compound, rhodium-containing compound, the non-aqueous solution choosing
From one of alcohol compound, ketone compounds, petroleum ether.
9. a kind of method for increasing production light aromatics, using any one catalyst described in claim 1~8, which is characterized in that
Reaction temperature is 100-500 DEG C, reaction pressure 0.5-8MPa, and hydrogen hydrocarbon molar ratio is 1-10, and feed weight air speed is 0.5-20.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710709603.2A CN109395716B (en) | 2017-08-18 | 2017-08-18 | Yield-increasing light aromatic hydrocarbon catalyst |
| KR1020180095695A KR102504661B1 (en) | 2017-08-18 | 2018-08-16 | Catalyst for producing light aromatics with heavy aromatics, method for preparing the catalyst, and use thereof |
| JP2018153138A JP7158953B2 (en) | 2017-08-18 | 2018-08-16 | Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof |
| BE2018/5572A BE1025972B1 (en) | 2017-08-18 | 2018-08-17 | CATALYST FOR PRODUCING LIGHT AROMATICS WITH HEAVY AROMATICS, PROCESS FOR PREPARING THE CATALYST AND USE THEREOF |
| DE102018213896.6A DE102018213896A1 (en) | 2017-08-18 | 2018-08-17 | Catalyst for the production of light aromatic substances with heavy aromatic substances, process for the preparation of the catalyst and use thereof |
| ES201830831A ES2700899B2 (en) | 2017-08-18 | 2018-08-17 | Catalyst for producing light aromatics with heavy aromatics, method of preparing the catalyst and use thereof |
| US16/105,293 US11065604B2 (en) | 2017-08-18 | 2018-08-20 | Catalyst for producing light aromatics with heavy aromatics, method for preparing the catalyst, and use thereof |
| FR1800885A FR3070130B1 (en) | 2017-08-18 | 2018-08-20 | CATALYST FOR PRODUCING LIGHT AROMATICS WITH HEAVY AROMATICS, METHOD FOR PREPARING THE CATALYST AND USE THEREOF |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103120955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons and preparation method thereof |
| CN104549465A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst |
| CN104645981A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Pyrolysis gasoline hydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103120955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons and preparation method thereof |
| CN104549465A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst |
| CN104645981A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Pyrolysis gasoline hydrogenation catalyst and preparation method thereof |
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