CN111097485A - Catalyst for catalyzing diesel oil hydrogenation conversion, preparation method and application thereof - Google Patents
Catalyst for catalyzing diesel oil hydrogenation conversion, preparation method and application thereof Download PDFInfo
- Publication number
- CN111097485A CN111097485A CN201811264077.4A CN201811264077A CN111097485A CN 111097485 A CN111097485 A CN 111097485A CN 201811264077 A CN201811264077 A CN 201811264077A CN 111097485 A CN111097485 A CN 111097485A
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- CN
- China
- Prior art keywords
- molecular sieve
- modified
- type molecular
- catalyst
- dealumination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 208
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 198
- 238000000034 method Methods 0.000 claims abstract description 64
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 52
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 30
- GDCCFQMGFUZVKK-UHFFFAOYSA-N 1-butyl-2h-pyridine Chemical compound CCCCN1CC=CC=C1 GDCCFQMGFUZVKK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000004898 kneading Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- -1 benzyl quaternary ammonium salt Chemical class 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229940104869 fluorosilicate Drugs 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 3
- OSPKGDDLQQVQSG-UHFFFAOYSA-M benzyl(tripropyl)azanium;bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 OSPKGDDLQQVQSG-UHFFFAOYSA-M 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 34
- 239000003502 gasoline Substances 0.000 abstract description 14
- 238000007142 ring opening reaction Methods 0.000 abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 14
- 238000005336 cracking Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 102100039339 Atrial natriuretic peptide receptor 1 Human genes 0.000 description 2
- IEYSWVWNWSRECJ-UHFFFAOYSA-N C(CCC)C1=NC=CC=C1.N1=CC=CC=C1 Chemical compound C(CCC)C1=NC=CC=C1.N1=CC=CC=C1 IEYSWVWNWSRECJ-UHFFFAOYSA-N 0.000 description 2
- 101000961044 Homo sapiens Atrial natriuretic peptide receptor 1 Proteins 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- JSOQIZDOEIKRLY-UHFFFAOYSA-N n-propylnitrous amide Chemical compound CCCNN=O JSOQIZDOEIKRLY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 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
- 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
- B01J29/084—Y-type faujasite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- 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
- B01J2029/081—Increasing the silica/alumina ratio; Desalumination
-
- 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
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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Abstract
The invention discloses a catalytic diesel oil hydroconversion catalyst, a preparation method and an application thereof, wherein the hydroconversion catalyst contains 30-70 wt% of modified Y-type molecular sieve and 0.01-0.1 wt% of carbon based on the total weight of the hydroconversion catalyst, the ratio of the infrared total acid content of pyridine and the infrared total acid content of n-butylpyridine in the modified Y-type molecular sieve is 1-1.2, the infrared total acid content of the pyridine is 0.1-1.2 mmol/g, and the modified Y-type molecular sieve contains Na based on the total weight of the modified Y-type molecular sieve20.5-2.0 w% of O, and the preparation method of the hydroconversion catalyst adopts a kneading method or an impregnation methodThe following method is preferred. The catalyst has excellent selective ring-opening conversion capability of polycyclic cyclic hydrocarbon and good reaction selectivity, can greatly improve the quality of gasoline and diesel products converted by catalyzing diesel hydrogenation, has higher yield of reaction liquid products, and has wide application prospect in the process of catalyzing diesel hydrogenation conversion reaction.
Description
Technical Field
The invention relates to a catalytic diesel oil hydro-conversion catalyst, a preparation method and application thereof, belonging to the field of hydro-conversion.
Background
Since the new century, along with the increasing enhancement of people's environmental awareness, the stricter of national environmental regulations and the rapid development of national economy, the demand of various countries in the world for clean motor fuels is increasing. The catalytic cracking (FCC) technology is one of the main technological means for heavy oil conversion, and plays an important role in oil refining enterprises of various countries in the world. The annual processing capacity of a catalytic cracking unit in China currently exceeds 1 hundred million tons, which is second only to the United states. In the gasoline and diesel oil products, the catalytic cracking gasoline accounts for about 80 percent, and the catalytic diesel oil accounts for about 30 percent. In recent years, with the increasing weight of the quality of domestic processed crude oil, the raw materials processed by catalytic cracking are also increasingly heavy and inferior, and in addition, in order to achieve the purpose of improving the quality of gasoline or increasing the yield of propylene, a plurality of enterprises modify a catalytic cracking unit or increase the operation severity of the catalytic cracking unit, so that the quality of products of catalytic cracking, particularly catalytic diesel oil, is more deteriorated.
In order to improve the utilization rate of petroleum resources, improve the overall quality level of gasoline and diesel fuel, realize the aims of optimizing product blending and maximizing product value and meet the continuously increasing demands for clean fuel in China, the novel hydro-conversion process technology for producing high-added-value naphtha components and low-sulfur clean diesel fuel by hydro-conversion of high-aromatic-hydrocarbon diesel has good application prospect. Researchers at home and abroad also carry out a great deal of research work. The catalytic cracking light cycle oil is converted into ultra-low sulfur diesel oil and a blending component of high octane gasoline by adopting a hydro-conversion process technology in foreign countries. Such as: NPRA annual meeting in 1995, David a. pappal et al introduced a single stage hydroconversion process technology developed by Mobil, Akzo Nobel/Nippon Ketjen and m.w. kellogg companies; the 2005 annual meeting of NPRA, Vasant P. Thakkar et al introduced the LCO Unicraking technology developed by UOP. Both of the above techniques have been reported to convert low value catalytic cycle oil components into high octane gasoline components and premium diesel blending components.
The core of the hydro-conversion technology is a hydro-conversion catalyst which is a bifunctional catalyst with cracking and hydrogenation activities, wherein the cracking function is provided by acidic carrier materials such as molecular sieves, the hydrogenation function is provided by active metals of a VI group and a VIII group in the periodic table of elements loaded on the catalyst, and different reaction requirements are met by modulating the cracking and hydrogenation double-function positions. The molecular sieve is used as a cracking component of the hydro-conversion catalyst, and the performance of the molecular sieve plays a decisive role in the reaction performance of the catalyst. The catalytic diesel oil hydro-conversion catalyst requires that the catalyst has good ring-opening reaction capability of cyclic hydrocarbon, and simultaneously, excessive secondary cracking reaction is required to be avoided, and the cracking of chain hydrocarbon and the chain scission reaction of alkyl naphthene after ring opening are reduced.
In the modified Y-type molecular sieve obtained by the existing modification method, acid centers are distributed in different pore channels of the molecular sieve (micropores and secondary pores), the availability of the acid centers in the micropores is poor, and on the other hand, excessive secondary cracking reaction is easily caused, the reaction selectivity and the product liquid yield are reduced, so that the quality and the liquid yield of the catalytic diesel hydro-conversion product are reduced.
US4503023 discloses a molecular sieve modification method, which adopts a liquid phase dealuminization and silicon supplementation mode of NaY zeolite with ammonium fluosilicate to prepare a molecular sieve with high crystallinity, high silica-alumina ratio and certain capability of resisting organic nitrogen poisoning, but because the structure is too complete, almost no secondary holes exist, the acid center is mainly located at the micropores, and the accessibility of macromolecular reactants in poor-quality raw materials is poor; patent CN96119840.0 adopts a hydrothermal desulfurization and buffer solution treatment combined mode to carry out modification treatment on a Y molecular sieve, and the obtained molecular sieve has abundant secondary pores and good diffusion performance, but the modified Y molecular sieve obtained by the modification mode still has a large number of acid sites in a microporous structure, the dispersity of the acid sites of the molecular sieve is large, and the reaction selectivity is poor; chinese patent CN96120016.2 discloses a high-silicon-crystallinity Y-type molecular sieve and a preparation method thereof, NH4NaY is used as a reaction raw material, ammonium hexafluorosilicate is firstly used for dealuminizing and silicon supplementing, then hydrothermal treatment is carried out, and finally aluminum salt solution treatment is carried out, so that the obtained Y molecular sieve keeps higher crystallinity while deep dealuminizing, but the content of secondary pores of the obtained modified Y molecular sieve is lower, and simultaneously, a large number of acid centers are distributed in micropores, so that excessive cracking reaction is caused in the reaction process, and the liquid yield is reduced; U.S. Pat. No. 4,327 discloses a hydroconversion process, wherein a modification process of a Y-type molecular sieve is disclosed, wherein the modification process comprises contacting the Y-type molecular sieve with at least 0.5psi of water vapor at 315-899 ℃ for a period of time to obtain a modified Y-type molecular sieve with a unit cell constant of 2.440-2.464 nm; performing ammonium exchange on the treated Y molecular sieve to obtain an intermediate with the sodium content of less than 1%; then, the modified Y molecular sieve with the unit cell constant less than 2.440nm is obtained, but the treatment process is harsh, so that the obtained modified Y molecular sieve has serious damage to the crystallinity and low crystallinity, and the service performance of the modified Y molecular sieve is influenced.
Aiming at the defects of the prior art, the invention provides the hydroconversion catalyst for producing the high-quality lube base oil raw material and the preparation method thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for catalyzing diesel oil to be subjected to hydroconversion and a preparation method and application thereof. The catalyst prepared by the method has excellent selective ring-opening conversion capability of polycyclic cyclic hydrocarbon and good reaction selectivity, can greatly improve the quality of gasoline and diesel products converted by catalyzing diesel hydrogenation, and has high yield of reaction liquid products and wide application prospect in the process of catalyzing diesel hydrogenation conversion reaction.
A catalytic diesel hydroconversion catalyst comprising from 10 to 45 wt%, preferably from 15 to 30 wt%, based on the total weight of the hydroconversion catalyst% of hydrogenation active metal calculated by metal oxide, 30-70 wt%, preferably 35-60 wt% of modified Y-type molecular sieve, 0.01-0.1 wt% of carbon, the ratio of the infrared total acid content of pyridine to the infrared total acid content of n-butylpyridine in the modified Y-type molecular sieve is 1-1.2, the infrared total acid content of pyridine is 0.1-1.2 mmol/g, and the modified Y-type molecular sieve contains Na based on the total amount of the modified Y-type molecular sieve2O 0.5~2.0w%。
Preferably, the balance of the catalytic diesel hydroconversion catalyst is selected from at least one of alumina, silica or amorphous silica-alumina.
Preferably, the specific surface area of the modified Y-type molecular sieve is 500-900m2(ii)/g; the pore volume of the modified Y-type molecular sieve is 0.28-0.7 ml/g; the relative crystallinity of the modified Y-type molecular sieve is 50-130%; the unit cell parameter of the modified Y-type molecular sieve is 2.425-2.450; the silicon-aluminum molar ratio of the modified Y-type molecular sieve is (6-80): 1.
a preparation method of a catalytic diesel oil hydroconversion catalyst is prepared by a kneading method or an impregnation method, and preferably by the following method:
(I) mixing at least one of alumina, silicon oxide or amorphous silicon-aluminum and the modified Y-shaped molecular sieve to obtain a mixed material, and then adding an acidic aqueous solution into the mixed material to prepare a slurry for extruding and molding;
(II) drying and roasting the extruded strip product obtained in the step (I);
and (III) performing saturated impregnation on the material obtained in the step (2) in a solution containing hydrogenation active metal, and drying and roasting the obtained product to obtain the hydroconversion catalyst.
In the method, in the step (I), 3-30 wt% of nitric acid aqueous solution is added, the solid content of the slurry is suitable for extrusion molding to obtain a strip-shaped extrusion product, and preferably, the solid content of the slurry is 30-60 wt%.
In the above method, the preparation method of the modified Y-type molecular sieve in step (I) comprises the following steps:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) dipping the pretreated Y molecular sieve obtained in the step (1) by adopting a macromolecular salt solution;
(3) carbonizing the Y molecular sieve subjected to the dipping treatment of the macromolecular salt solution in the step (2) in an oxygen-free environment;
(4) performing sodium ion exchange treatment on the molecular sieve in the step (3);
(5) and (4) drying and roasting the treated molecular sieve in the step (4) to prepare a final Y molecular sieve product.
Preferably, the pretreatment in step (1) comprises: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination.
Preferably, the pretreatment in step (1) comprises:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) and carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium-removed and dealuminated Y-shaped molecular sieve, wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
The method, step (II), is drying at 80-120 ℃ for 1-5h, and then calcining at 400-500 ℃ for 1-5 h.
The amount of the solution containing the hydrogenation active metal added in step (III) of the above process may be such that the resulting hydroconversion catalyst contains the active metal in an amount of from 10 to 45% by weight, preferably from 15 to 30% by weight, calculated as metal oxide. The concentration of the active metal in the active metal-containing solution may be 20 to 50% by weight in terms of metal oxide. The active metal-containing solution may be a solution of a compound containing a metal element of group VIII and/or group VI. Preferably, it may be a solution of a compound containing Ni and/or Co, a solution of a compound containing W and/or Mo. More preferably, the solution containing the active metal may be a solution containing nickel nitrate, cobalt nitrate, ammonium metatungstate, ammonium molybdate, molybdenum oxide.
In the method, the drying in the step (III) can be completed at 90-150 ℃ for 2-20 h. The roasting can be completed at 400-600 ℃ for 2-10 h. The active metal is converted to the oxide form present in the hydroconversion catalyst.
A catalytic diesel hydroconversion process, comprising: in the presence of hydrogen, catalytic diesel oil is contacted with the hydroconversion catalyst to carry out the hydroconversion reaction, wherein the reaction temperature is 340--1The volume ratio of the hydrogen to the catalytic diesel is (200- & 2000): 1. the preferred catalytic diesel oil has the distillation range of 200-380 ℃ and the density of 0.88-0.96 g/cm3。
Through the technical scheme, the invention provides the modified Y-type molecular sieve with the acidic central position intensively distributed in a large pore channel (namely a secondary pore). The acid center position in the micropores of the modified Y-type molecular sieve is basically occupied by sodium ions, only the acid center in the macropore is left, and the occurrence of secondary cracking reaction when hydrocarbon molecules enter the micropores can be reduced. By measuring the infrared acid content on the modified Y-type molecular sieve by using basic organic matters with different molecular sizes, such as pyridine and n-butylpyridine, when the acid content values of the two are equivalent, the distributed acid centers in the modified Y-type molecular sieve can be shown to be concentrated in a large pore channel.
The invention provides a method for preparing a modified Y-type molecular sieve, which comprises the steps of firstly carrying out benzyl quaternary ammonium salt solution dipping treatment on an acid center of the modified Y-type molecular sieve, and selectively distributing benzyl quaternary ammonium salt in a macropore in the step of benzyl quaternary ammonium salt treatment by utilizing the fact that the benzyl quaternary ammonium salt has larger molecular size. And then carrying out anaerobic carbonization on the Y molecular sieve subjected to benzyl quaternary ammonium salt impregnation treatment to ensure that the benzyl quaternary ammonium salt is carbonized in situ and in a large pore to block a pore channel of the large pore, selectively shielding acid centers distributed in small pores of the Y molecular sieve by subsequent sodium ion exchange treatment, and finally roasting to obtain the molecular sieve with the acid center positions distributed in the large pore channel. The molecular sieve is used for the preparation process of the catalyst for the hydrogenation and modification of the diesel oil, the selective ring-opening conversion capability of the catalyst on aromatic compounds can be obviously improved, the occurrence of secondary cracking reaction is reduced, more long-chain paraffin is enriched in the hydrogenation and conversion diesel oil product, and more monocyclic aromatic hydrocarbon is enriched in the gasoline product, so that the quality of the gasoline and the diesel oil is obviously improved, and the yield of liquid products is improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The modified Y-type molecular sieve contains 0.5-2 wt% of Na based on the total amount of the modified Y-type molecular sieve2O; the ratio of the infrared total acid content of pyridine to the infrared total acid content of n-butylpyridine in the Y-type molecular sieve is 1-1.2; the total infrared acid content of pyridine is 0.1-1.2 mmol/g, the carbon content is 0.02-0.1%,
the modified Y-type molecular sieve provided by the invention has the advantages that the acidic centers are mainly distributed in the macropores, and a small amount of even no acidic centers are distributed in the micropores, so that secondary cracking reaction of hydrocarbon oil molecules entering the micropores on the acidic centers can be reduced.
The characteristic of the distribution of the acid centers in the pore channels of the modified Y-type molecular sieve provided by the invention can be embodied by using pyridine and n-butylpyridine as two probe molecules to respectively perform acid measurement on the modified Y-type molecular sieve. The molecular diameter of n-butylpyridine is about 0.8nm, and can only enter the large pore channel of the modified Y-type molecular sieve provided by the invention to reflect the total amount of acid centers in the large pore channel. The molecular diameter of pyridine is about 0.6nm, and the pyridine can enter micropores and macropores of the modified Y-type molecular sieve to reflect the total amount of acid centers in all the pores of the modified Y-type molecular sieve. The specific test process may be: by pyridine and n-butylpyridine absorption infrared spectroscopy, a Nicolet 6700 Fourier infrared spectrometer of the Nicolet company in America is adopted,
taking 20mg of a ground sample (the granularity is less than 200 meshes), pressing into a sheet with the diameter of 20mm, and mounting the sheet on a sample rack of an absorption cell; a 200mg sample (sheet) was loaded into a beaker at the lower end of the quartz spring (the spring length was recorded before the sample was loaded,x 1mm), connecting the absorption cell with an adsorption tube, and starting to evacuate and purify to reach a vacuum degree of 4 multiplied by 10-2At Pa, the temperature was raised to 500 ℃ and maintained for 1 hour to remove adsorbed substances on the surface of the sample (in this case, the length of the spring after sample purification is recorded,x 2mm). Then cooling to room temperature, adsorbing pyridine (or n-butylpyridine) to saturation, heating to 160 ℃, balancing for 1 hour, desorbing the physically adsorbed pyridine (at this time, the length of the spring after adsorbing the pyridine,x 3mm), the total acid amount was determined by a pyridine (or n-butylpyridine) gravimetric adsorption method.
The invention adjusts the concentrated distribution of the acid center position in the micropores and macropores of the Y-shaped molecular sieve, thereby realizing the control of the reaction of hydrocarbon oil molecules on the molecular sieve. And the distribution of the acid center position is represented by the infrared acid total amount measurement of pyridine and n-butylpyridine. For a conventional Y-type molecular sieve which is not subjected to acid center position adjustment in a pore channel, the ratio of the infrared total acid amount of pyridine to the infrared total acid amount of n-butylpyridine is larger than 1.2. Thereby distinguishing whether the acid center position in the micropores of the Y-type molecular sieve is controlled.
When the total acid amount of the modified Y-type molecular sieve measured by respectively using n-butylpyridine and pyridine is equal to or slightly smaller than that of n-butylpyridine, namely the ratio of the infrared total acid amount of pyridine of the modified Y-type molecular sieve to the infrared total acid amount of n-butylpyridine of the modified Y-type molecular sieve is 1-1.2, the modified Y-type molecular sieve is proved to contain mainly concentrated acid centers in a large pore channel.
According to the present invention, preferably, the modified Y-type molecular sieve contains 0.8-1.8 wt% of Na based on the total amount of the modified Y-type molecular sieve2O; the ratio of the infrared total acid content of pyridine to the infrared total acid content of n-butylpyridine in the Y-type molecular sieve is 1.02-1.15; the carbon content is 0.02-0.08%.
More preferably, the Y-type molecular sieve contains 1-1.5 wt% of Na based on the total amount of the Y-type molecular sieve2O; the ratio of the pyridine infrared total acid amount of the Y-type molecular sieve to the n-butylpyridine infrared total acid amount of the Y-type molecular sieve is 1.05-1.12; the carbon content is 0.03-0.07%
According to the invention, the pyridine infrared total acid content of the Y-type molecular sieve is preferably 0.2-1 mmol/g.
More preferably, the total pyridine infrared acid content of the Y-type molecular sieve is 0.3-0.8 mmol/g.
According to the invention, the modified Y-type molecular sieve has other characteristics, and is also favorable for catalyzing the diesel oil hydrogenation conversion reaction process, improving the quality of gasoline and diesel oil products and increasing the yield of liquid products. Preferably, the specific surface area of the Y-type molecular sieve is 500-900m2(ii)/g; preferably 550-850m2(ii)/g; more preferably 600-750m2/g。
Preferably, the pore volume of the Y-type molecular sieve is 0.28-0.7 ml/g; preferably 0.3-0.65 ml/g; more preferably 0.35-0.6 ml/g.
Preferably, the relative crystallinity of the Y-type molecular sieve is 50-130%; 60% -110%; more preferably 70% to 100%.
Preferably, the unit cell parameters of the Y-type molecular sieve are 2.425-2.45 nm; preferably 2.428-2.448 nm; more preferably from 2.43 to 2.445 nm.
Preferably, the Y-type molecular sieve has a silica-alumina molar ratio of (6-80): 1; preferably (8-60): 1; more preferably (10-50): 1.
a method for preparing the Y-type molecular sieve of the present invention, comprising the steps of:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) dipping the pretreated Y molecular sieve obtained in the step (1) by adopting a macromolecular salt solution;
(3) carbonizing the Y molecular sieve subjected to the dipping treatment of the benzyl quaternary ammonium salt solution in the step (2) in an oxygen-free environment;
(4) performing sodium ion exchange treatment on the molecular sieve in the step (3);
(5) and (4) drying and roasting the treated molecular sieve in the step (4) to prepare a final Y molecular sieve product.
According to the invention, the step (1) is used for forming large pore channels in the NaY molecular sieve, and is helpful for respectively modifying the large pore channels and the small pore channels in the follow-up process. Preferably, the pretreatment in step (1) comprises: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination. In the present invention, the NaY molecular sieve may be subjected to one or more steps of ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination, and the order between the steps may not be limited as long as the sodium-removed and dealuminated Y molecular sieve can be provided, for example, Na of the sodium-removed and dealuminated Y molecular sieve2O content less than 3 wt%, SiO2/Al2O3The molar ratio is (6-80): 1. unit cell constants 2.425-2.450. Generally, the NaY molecular sieve is first sodium-removed by ammonium ion exchange, and then the sodium-removed product is dealuminized, which may be one or a combination of hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination.
In a preferred embodiment of the present invention, the pretreatment in step (1) comprises:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium and aluminum removed Y-shaped molecular sieve,
wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
According to the invention, the step (a) is used for removing Na ions in the NaY molecular sieve, so that the subsequent dealumination process can be smoothly carried out. Preferably, the process of the ammonium salt ion exchange reaction in step (a) is as follows: exchanging the NaY molecular sieve with an ammonium salt aqueous solution for 1-3h at 60-120 ℃, preferably 60-90 ℃, wherein the exchange times are 1-4 times, and obtaining the sodium-removed Y-type molecular sieve.
Preferably, Na of the sodium-removed Y-type molecular sieve2The O content is less than 3 wt.%.
Preferably, the SiO of the NaY molecular sieve2/Al2O3The molar ratio is (3-6): 1, Na2The O content is 6-12 wt%.
Preferably, the ammonium salt is selected from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the molar concentration of the ammonium salt aqueous solution is 0.3-6mol/L, preferably 1-3 mol/L.
According to the invention, step (b) is used for dealuminating the sodium-removed Y-type molecular sieve to form macropores. Preferably, the hydrothermal dealumination in step (b) is carried out by: contacting the sodium-removed Y-type molecular sieve with steam for 1-6h at the temperature of 520-700 ℃ and the pressure of 0.01-0.5 MPa.
Preferably, the number of times of the hydrothermal dealumination is 1 to 3 times.
According to the invention, step (c) is used for the chemical dealumination of molecular sieves, forming macropores. Preferably, the chemical dealumination in step (c) is performed by: and (3) carrying out constant-temperature reaction on the product of the hydrothermal dealumination and an aluminum salt solution, an ammonium fluosilicate solution or a nitric acid solution at the temperature of 50-120 ℃ for 0.5-3 h.
Preferably, the aluminum salt solution is an aqueous solution of at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate.
Preferably, the molar concentration of the aluminum salt solution, the ammonium fluosilicate solution or the nitric acid solution is 0.05-2 mol/L. And (3) carrying out the constant temperature reaction on the product of the hydrothermal dealumination and the aluminum salt solution to obtain the aluminum salt dealumination. And when the product of the hydrothermal dealumination and the ammonium fluosilicate solution are subjected to the constant temperature reaction, the dealumination of the fluosilicate is obtained. And when the product of the hydrothermal dealumination and the nitric acid solution are subjected to the constant temperature reaction, the acid dealumination is obtained.
According to the invention, the macromolecular salt solution dipping treatment step in the step (2) is to selectively occupy the large pores of the Y molecular sieve pretreated in the step (1) by utilizing the characteristic of large molecular size of macromolecular ammonium salt, then the Y molecular sieve subjected to the benzyl quaternary ammonium salt dipping treatment is subjected to an oxygen-free carbonization step, so that the benzyl quaternary ammonium salt is carbonized in situ in the large pores to block the pore channels of the large pores, the subsequent sodium ion exchange treatment selectively shields the acid centers distributed in the small pores of the Y molecular sieve, and finally the acid centers obtained by roasting treatment are concentrated in the large pores. Preferably, the impregnation treatment in step (3) is carried out by: and (3) soaking the sodium-containing Y-type molecular sieve in the macromolecular ammonium salt solution for 2-6h at 40-80 ℃.
In the present invention, preferably, the macromolecular ammonium salt is benzyl quaternary ammonium salt.
Preferably, the benzyl quaternary ammonium salt is at least one of benzyl tripropyl ammonium bromide, benzyl tributyl ammonium bromide, benzyl tripropyl ammonium chloride and benzyl tributyl ammonium chloride.
Preferably, the molar concentration of the macromolecular ammonium salt solution is 0.2-2mol/L based on the concentration of bromine or chlorine in the macromolecular ammonium salt solution.
In the invention, the distribution of acid centers in the prepared Y-type molecular sieve can be measured by adopting a pyridine infrared adsorption and n-butylpyridine infrared adsorption method. The specific method and test results are as described above and will not be described in detail.
According to the present invention, preferably, the oxygen-free environment of the oxygen-free carbonization treatment step in step (3) may be an inert gas atmosphere such as nitrogen, carbon dioxide, helium, etc.; reaction conditions are as follows: the temperature is 500-700 ℃; the time is 4-20 h.
According to the invention, preferably, the sodium ion exchange treatment process in the step (4) is to add the Y molecular sieve subjected to the oxygen-free carbonization treatment in the step (3) into the solution with the concentration of 0.1-3.0 wt%Na（NO3) Heating the mixture to 40-80 ℃ in the aqueous solution, and reacting for 1-4 h at constant temperature.
According to the invention, preferably, the drying condition in the step (5) is 100-150 ℃, and the drying is carried out for 1-4 h; the roasting condition is 500-700 ℃ for 4-8 h.
In the invention, the hydro-conversion catalyst contains the modified Y-type molecular sieve component, so that the ring-opening conversion efficiency of aromatic hydrocarbons, especially aromatic hydrocarbons with more than two rings, in catalytic diesel oil can be obviously improved, the occurrence of secondary cracking reaction is reduced, the selectivity of products of the hydro-conversion reaction is better, and the quality of gasoline and diesel oil products is higher. The reaction performance of the hydroconversion catalyst may be determined by specific reaction performance evaluation experiments. The experiment can adopt a single-stage series one-time pass process flow on a small micro-reactor, the device is provided with two reactors connected in series, the first reactor is filled with a conventional refined catalyst, and the second reactor is filled with a hydroconversion catalyst along the flow sequence.
In the invention, the second reactor is filled with the hydro-conversion catalyst of the invention for one time and filled with the hydro-conversion catalyst prepared by the conventional Y-shaped molecular sieve for the other time, reaction evaluation is respectively carried out, and the cetane number of a diesel product, the octane number of a gasoline product and the yield of a liquid product of the device are respectively obtained by two reactions. Wherein, the higher the octane number of the gasoline product, the higher the cetane number of the diesel oil product and the higher the yield of the reaction liquid product, the higher the corresponding catalyst is in the process of carrying out the hydro-conversion reaction, thereby promoting the ring-opening conversion reaction of the aromatic hydrocarbon compound and reducing the occurrence of the secondary cracking reaction.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the amounts of pyridine and n-butylpyridine in infrared are determined by pyridine and n-butylpyridine absorption infrared spectroscopy, using Nicolet 6700 Fourier transform infrared spectrometer of Nicolet, USA, and the procedure is as follows:
pressing 20mg of ground sample (granularity less than 200 meshes) into a sheet with the diameter of 20mm, placing the sheet on a sample rack of an absorption cell, placing 200mg of sample (sheet) into a hanging cup at the lower end of a quartz spring(the spring length is recorded before the sample is applied,x 1mm), connecting the absorption cell with an adsorption tube, and starting to evacuate and purify to reach a vacuum degree of 4 multiplied by 10-2At Pa, the temperature was raised to 500 ℃ and maintained for 1 hour to remove adsorbed substances on the surface of the sample (in this case, the length of the spring after sample purification is recorded,x 2mm). Then cooling to room temperature, adsorbing pyridine (n-butylpyridine) to saturation, heating to 160 ℃, balancing for 1 hour, desorbing the physically adsorbed pyridine (at this time, the length of the spring after adsorbing the pyridine,x 3mm), the total acid amount was determined by a pyridine (n-butylpyridine) gravimetric adsorption method.
The surface area and pore volume were measured by using a low-temperature nitrogen adsorption method (BET method);
na in molecular sieve2O content, molecular Sieve SiO2/Al2O3The molar ratio was determined by fluorimetry;
the unit cell parameters and the relative crystallinity of the molecular sieve are determined by an XRD method, the instrument is a Rigaku Dmax-2500X-ray diffractometer, Cuk α radiation is adopted, graphite single crystal filtering is carried out, the operating tube voltage is 35KV, the tube current is 40mA, the scanning speed (2 theta) is 2 DEG/min, the scanning range is 4 DEG-35 DEG, and a standard sample is the Y-type molecular sieve raw powder used in the embodiment 1 of the invention.
Example 1
Modification treatment process of the molecular sieve:
(1) mixing NaY molecular sieve raw powder (Na2O content is 10 wt%, SiO2/Al2O 3mol ratio is 5.0) prepared in a laboratory with ammonium nitrate with concentration of 1.0mol/L according to liquid-solid ratio of 3:1, exchanging at 70 ℃ for 3 hours, repeating the process for 3 times, wherein Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 550 ℃ and 0.1MPa for 2 hours; this process was repeated once.
(3) And (3) mixing the molecular sieve obtained in the step (2) with 0.5mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, heating to 80 ℃, and reacting for 2 hours at constant temperature.
(4) Step (3) passing through Na (NO)3) The treated Y molecular sieve is added at the concentration ofTreating the mixture for 3 hours at the temperature of 70 ℃ in 0.5mol/L aqueous solution of benzyl tributyl ammonium bromide;
(5) treating the molecular sieve in the step (4) at 550 ℃ for 15h in a nitrogen atmosphere;
(6) adding the Y molecular sieve treated by the aluminum salt obtained in the step (5) to 0.8mol/L of Na (NO)3) Treating with water solution at 60 deg.C for 2 hr;
(7) and (4) drying the molecular sieve in the step (6) at 120 ℃ for 4h, and roasting at 550 ℃ for 6h to obtain the modified Y molecular sieve in the example 1, wherein the molecular sieve is numbered as Y-1.
Example 2
(1) Taking NaY molecular sieve raw powder (the content of Na2O is 10 weight percent, the molar ratio of SiO2/Al2O3 is 5.0) prepared in a laboratory, mixing the raw powder with ammonium nitrate with the concentration of 2.0mol/L according to the liquid-solid ratio of 3:1, exchanging for 2 hours at 80 ℃, repeating the process for 1 time, wherein the Na content in the exchanged Y molecular sieve is 2.7 percent calculated by Na 2O.
(2) Carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 580 ℃ under 0.1Mpa for 2 h.
(3) Treating the molecular sieve obtained in the step (2) for 2 hours at 90 ℃ according to a liquid-solid ratio of 5:1 and an ammonium fluosilicate solution with the concentration of 0.3 mol/L;
(4) adding the Y molecular sieve into 1.5mol/L benzyl tributyl ammonium chloride aqueous solution, and treating for 3h at 80 ℃;
(5) treating the molecular sieve at 600 ℃ for 8h under the atmosphere of helium;
(6) adding the step (5) to 2.0mol/L of Na (NO)3) Treating with water solution at 80 deg.C for 2 hr;
(7) and (4) drying the molecular sieve in the step (6) at 120 ℃ for 4h, and roasting at 600 ℃ for 5h to obtain the modified Y molecular sieve in the example 2, wherein the molecular sieve is numbered as Y-2.
Example 3
(1) Mixing NaY molecular sieve raw powder (Na2O content is 10 wt%, SiO2/Al2O 3mol ratio is 5.0) prepared in a laboratory with ammonium nitrate with concentration of 2.0mol/L according to liquid-solid ratio of 3:1, exchanging at 80 ℃ for 2 hours, repeating the process for 2 times, wherein Na content in the exchanged Y molecular sieve is Na22.3 percent of O;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 600 ℃ and 0.1MPa for 1 hour.
(3) And (3) mixing the molecular sieve obtained in the step (2) with 0.4mol/L dilute nitric acid solution according to the liquid-solid ratio of 5:1, heating to 80 ℃, and reacting at constant temperature for 2 hours.
(4) Step (3) passing through Na (NO)3) Adding the treated Y molecular sieve into a 1.2mol/L aqueous solution of benzyltripropylammonium bromide, and treating for 2 hours at the temperature of 80 ℃;
(5) treating the molecular sieve at 650 ℃ for 6h in the atmosphere of carbon dioxide;
(6) adding the Y molecular sieve obtained in the step (5) into 1.5mol/L Na (NO)3) Treating with water solution at 70 deg.C for 2 hr;
(7) and (4) drying the molecular sieve in the step (6) at 120 ℃ for 4h, and roasting at 650 ℃ for 4h to obtain the modified Y molecular sieve in the embodiment 3, wherein the molecular sieve is numbered as Y-3.
Example 4
(1) Mixing NaY molecular sieve raw powder (Na2O content is 10 wt%, SiO2/Al2O 3mol ratio is 5.0) prepared in a laboratory with ammonium nitrate with concentration of 0.5mol/L according to liquid-solid ratio of 3:1, exchanging at 70 ℃ for 3 hours, repeating the process for 3 times, wherein Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) treating the Y molecular sieve obtained in the step (1) with 0.2mol/L ammonium fluosilicate treatment solution according to the liquid-solid ratio of 6:1 at the constant temperature of 80 ℃ for 2 h;
(3) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (2) at 520 ℃ for 2h under 0.2MPa, and repeating the process for 1 time;
(4) and (4) stirring and mixing the molecular sieve obtained in the step (3) with 0.6mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, heating to 75 ℃, and reacting for 2 hours at constant temperature.
(5) Adding the Y molecular sieve into 0.5mol/L aqueous solution of benzyltributylammonium bromide, and treating for 5 hours at 60 ℃;
(6) treating the Y molecular sieve obtained in the step (5) at the high temperature of 550 ℃ for 18h in a nitrogen atmosphere;
(7) and (4) drying the molecular sieve in the step (6) at 120 ℃ for 4h, and roasting at 550 ℃ for 7h to obtain the modified Y molecular sieve in the example 4, wherein the number of the modified Y molecular sieve is Y-4.
Comparative example 1
(1) Mixing NaY molecular sieve raw powder prepared in a laboratory with ammonium nitrate with the concentration of 0.5mol/L according to the liquid-solid ratio of 3:1, exchanging for 3 hours at 70 ℃, repeating the process for 3 times, wherein the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1) at 550 ℃ and 0.1MPa for 2 hours; this process was repeated once.
(3) And (3) mixing the molecular sieve obtained in the step (2) with 0.5mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, and reacting for 2 hours at a constant temperature of 80 ℃.
And (3) drying the molecular sieve treated by the aluminum salt at 120 ℃ for 4h and roasting at 550 ℃ for 4h to obtain the modified Y molecular sieve of the comparative example 1, wherein the molecular sieve is numbered as B-1.
Comparative example 2
(1) 200g of NaY molecular sieve raw powder prepared in a laboratory is taken, ammonium nitrate with the concentration of 0.5mol/L is mixed according to the liquid-solid ratio of 3:1, the exchange is carried out for 3 hours at 70 ℃, the process is repeated for 3 times, and the Na content in the exchanged Y molecular sieve is Na2O is 2.5%;
(2) treating the Y molecular sieve obtained in the step (1) with 0.2mol/L ammonium fluosilicate treatment solution according to the liquid-solid ratio of 6:1 at the constant temperature of 80 ℃ for 2 h;
(3) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (2) at 520 ℃ for 2h under 0.2MPa, and repeating the process for 1 time;
(4) and (4) mixing the molecular sieve obtained in the step (3) with 0.6mol/L aluminum sulfate solution according to the liquid-solid ratio of 5:1, and reacting for 2 hours at a constant temperature of 75 ℃. The modified Y molecular sieve of comparative example 2, numbered B-2, was obtained after drying at 120 ℃ for 4h and calcining at 550 ℃ for 4 h.
The properties of the molecular sieves prepared in the above examples and comparative examples are shown in Table 1.
TABLE 1 comparison of physicochemical Properties of molecular sieves for examples and comparative examples
Example 5
The modified Y-type molecular sieves prepared in examples 1-4 and comparative examples 1-2 were used to prepare hydroconversion catalysts having the following formulation as shown in Table 2:
(1) mixing the modified Y-type molecular sieve and alumina to obtain a carrier mixed material, and adding a nitric acid aqueous solution with the mass fraction of 20 wt% into the carrier mixed material to prepare a slurry for extruding and forming;
(2) drying the extruded product obtained in the step (1) at 100 ℃ for 3h, and then roasting at 450 ℃ for 3h to obtain a silicon-aluminum carrier;
(3) and (3) saturating and dipping the silicon-aluminum carrier in a solution containing active metal, and drying and roasting the obtained product to obtain the hydroconversion catalyst.
The obtained catalyst is correspondingly numbered as: catalysts corresponding to the modified Y-type molecular sieves Y-1 to Y-4 of examples 1-4 were C-1 to C-4; the catalysts corresponding to the modified Y-type molecular sieves B-1 to B-3 of comparative examples 1-2 were BC-1 to BC-2. See table 2.
TABLE 2
Evaluation example 1
The catalysts C-1 to C-4 and BC-1 to BC-3 were subjected to evaluation tests on a small-scale microreaction device, the evaluation device adopted a single-stage tandem one-pass process, the first reactor was filled with a conventional refined catalyst, the second reactor was filled with the hydroconversion catalyst shown in Table 2, the properties of the reaction feed oil are shown in Table 3, and the evaluation results are shown in tables 4 to 5.
TABLE 3 Properties of the feedstock.
Table 4 example catalyst operating conditions.
Table 5 comparative example catalyst operating conditions.
Table 6 catalyst evaluation results of examples.
Table 6 evaluation results of catalysts of comparative examples
Claims (17)
1. A catalytic diesel hydroconversion catalyst, characterized by: the hydroconversion catalyst comprises, by taking the total weight of the hydroconversion catalyst as a reference, 10-45 wt% of hydrogenation active metal calculated by metal oxide, 30-70 wt% of modified Y-type molecular sieve and 0.01-0.1 wt% of carbon, wherein the ratio of the infrared total acid content of pyridine to the infrared total acid content of n-butylpyridine in the modified Y-type molecular sieve is 1-1.2, the infrared total acid content of pyridine is 0.1-1.2 mmol/g, and the modified Y-type molecular sieve contains Na based on the total weight of the modified Y-type molecular sieve2O 0.5~2.0w%。
2. The catalyst of claim 1, wherein: the hydrogenation conversion catalyst contains 15-30 wt% of hydrogenation active metal calculated by metal oxide and 35-60 wt% of modified Y-type molecular sieve based on the total weight of the hydrogenation conversion catalyst.
3. The catalyst of claim 1, wherein: the balance of the hydroconversion catalyst is selected from at least one of alumina, silica or amorphous silica-alumina.
4. The catalyst of claim 1, wherein: the specific surface area of the modified Y-type molecular sieve is 500-900m2(ii)/g; the above-mentionedThe pore volume of the modified Y-type molecular sieve is 0.28-0.7 ml/g; the relative crystallinity of the modified Y-type molecular sieve is 50-130%; the unit cell parameter of the modified Y-type molecular sieve is 2.425-2.450; the silicon-aluminum molar ratio of the modified Y-type molecular sieve is (6-80): 1.
5. a preparation method of a hydro-conversion catalyst is characterized by comprising the following steps: the hydro-conversion catalyst is prepared by a kneading method or an impregnation method.
6. The method of claim 5, wherein: the preparation method specifically comprises the following steps:
(I) mixing at least one of alumina, silicon oxide or amorphous silicon-aluminum and the modified Y-shaped molecular sieve to obtain a mixed material, and then adding an acidic aqueous solution into the mixed material to prepare a slurry for extruding and molding;
(II) drying and roasting the extruded strip product obtained in the step (I);
and (III) performing saturated impregnation on the material obtained in the step (2) in a solution containing hydrogenation active metal, and drying and roasting the obtained product to obtain the hydroconversion catalyst.
7. The method of claim 6, wherein: in the step (I), adding a nitric acid aqueous solution with the mass fraction of 3-30 wt%, wherein the solid content of the slurry is 30-60 wt%.
8. The method of claim 6, wherein: the preparation method of the modified Y-type molecular sieve in the step (I) comprises the following steps:
(1) pretreating a NaY molecular sieve to obtain a sodium-removed and aluminum-removed Y-type molecular sieve;
(2) dipping the pretreated Y molecular sieve obtained in the step (1) by adopting a macromolecular salt solution;
(3) carbonizing the Y molecular sieve subjected to the dipping treatment of the macromolecular salt solution in the step (2) in an oxygen-free environment;
(4) performing sodium ion exchange treatment on the molecular sieve in the step (3);
(5) and (4) drying and roasting the treated molecular sieve in the step (4) to prepare a final Y molecular sieve product.
9. The method of claim 8, wherein: the pretreatment process in the step (1) comprises the following steps: ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, and acid dealumination.
10. The method of claim 9, wherein: the pretreatment process in the step (1) comprises the following steps:
(a) carrying out ammonium ion exchange reaction on the NaY molecular sieve and an ammonium salt water solution to obtain a sodium-removed Y-type molecular sieve;
(b) carrying out hydrothermal dealumination on the sodium-removed Y-shaped molecular sieve to obtain a hydrothermal dealumination product;
(c) and carrying out chemical dealumination on the hydrothermal dealumination product to obtain the sodium-removed and dealuminated Y-shaped molecular sieve, wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination or acid dealumination.
11. The method of claim 8, wherein: the macromolecular salt is macromolecular ammonium salt.
12. The method of claim 11, wherein: the macromolecular ammonium salt is benzyl quaternary ammonium salt, and the molar concentration of the macromolecular ammonium salt solution is 0.2-2mol/L by the concentration of bromine or chlorine in the macromolecular ammonium salt solution.
13. The method of claim 12, wherein: the benzyl quaternary ammonium salt is at least one of benzyl tripropyl ammonium bromide, benzyl tributyl ammonium bromide, benzyl tripropyl ammonium chloride and benzyl tributyl ammonium chloride.
14. The method of claim 6, wherein: in the step (II), drying is carried out for 1-5h at 80-120 ℃, and then roasting is carried out for 1-5h at 400-500 ℃.
15. The method of claim 6, wherein: and (3) drying at 90-150 ℃ for 2-20 h, and roasting at 400-600 ℃ for 2-10 h.
16. A catalytic diesel oil hydroconversion method is characterized in that: the method comprises the following steps: in the presence of hydrogen, contacting the catalyst with the catalyst of any one of claims 1 to 4 to perform a hydroconversion reaction, wherein the reaction temperature is 340-420 ℃, the reaction pressure is 6-12MPa, and the volumetric air velocity of the catalytic diesel oil feed is 0.1-2h-1The volume ratio of the hydrogen to the catalytic diesel is (200- & 2000): 1.
17. the method of claim 16, wherein: the catalytic diesel oil has a distillation range of 200-380 ℃ and a density of 0.88-0.96 g/cm3。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111097487A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for catalyzing diesel oil hydrogenation modification and preparation method and application thereof |
| CN111097483A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Y molecular sieve and preparation method thereof |
| CN116062766A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097487A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for catalyzing diesel oil hydrogenation modification and preparation method and application thereof |
| CN111097483A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Y molecular sieve and preparation method thereof |
| CN116062766A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
| CN116062766B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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