CN113477247B - High-activity hydrothermal-resistant stable catalyst and preparation method thereof - Google Patents
High-activity hydrothermal-resistant stable catalyst and preparation method thereof Download PDFInfo
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- CN113477247B CN113477247B CN202111040727.9A CN202111040727A CN113477247B CN 113477247 B CN113477247 B CN 113477247B CN 202111040727 A CN202111040727 A CN 202111040727A CN 113477247 B CN113477247 B CN 113477247B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 230000000694 effects Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 110
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 43
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 239000010703 silicon Substances 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002808 molecular sieve Substances 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000499 gel Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000017 hydrogel Substances 0.000 claims description 16
- 239000000295 fuel oil Substances 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- -1 rare earth metal salt Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 238000004523 catalytic cracking Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims description 2
- JNTFBANTXBJKFO-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Mn+2].S(O)(O)(=O)=O.[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Mn+2].S(O)(O)(=O)=O.[N+](=O)([O-])[O-] JNTFBANTXBJKFO-UHFFFAOYSA-N 0.000 claims description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000001879 gelation Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 28
- 150000003624 transition metals Chemical class 0.000 abstract description 28
- 238000002715 modification method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- 239000011148 porous material Substances 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000007598 dipping method Methods 0.000 description 20
- 238000011282 treatment Methods 0.000 description 17
- 238000010335 hydrothermal treatment Methods 0.000 description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000013335 mesoporous material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000009718 spray deposition Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 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 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000003027 oil sand Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
- 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 invention discloses a high-activity hydrothermal-stability-resistant catalyst and a preparation method thereof. The high-activity hydrothermal-stability-resistant catalyst is prepared by mixing high-activity hydrothermal-stability-resistant catalyst powder, a binder and a forming auxiliary agent, preparing the mixture into a spherical or strip-shaped catalyst by using a forming device, and drying and roasting the spherical or strip-shaped catalyst; wherein the high-activity waterproof thermal stability catalyst powder comprises 0.02-20 wt% of covering component, 0.02-10 wt% of doping metal, 0.02-10 wt% of rare earth metal and 60-99.4 wt% of precursor in percentage by mass; the precursor gel is treated by surface covering, metal doping and rare earth modification methods, the water-resistant thermal stability of the catalyst is improved, the metal active center of the catalyst is increased by using transition metal and rare earth metal, and the high activity and high temperature-resistant hydrothermal stability of the catalyst are realized. After the high-activity water-resistant thermal-stability catalyst is treated under a high-temperature hydrothermal condition, the specific surface area is 200-390 m2The catalyst has good activity and hydrothermal stability, and is suitable for catalytic reaction under high-temperature hydrothermal process conditions.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a high-activity high-temperature-resistant hydrothermal stability catalyst and a preparation method thereof.
Background
The catalyst is the soul of catalytic technology and is also a key core material in the chemical industry, and the porous material is the most common catalytic material, such as a mesoporous molecular sieve catalyst, a microporous molecular sieve catalyst, a macroporous alumina catalyst and the like, and has high activity in the catalytic reaction process due to the developed pore structure and high specific surface advantage, so that the catalyst has wide application prospects in many fields. In general, the above-mentioned high-activity catalytic material has poor hydrothermal stability, and is particularly likely to undergo skeleton collapse under high-temperature hydrothermal conditions (> 800 ℃), thereby causing destruction of the entire material structure. The current high-activity catalytic materials have poor hydrothermal stability, so that the application of the high-activity catalytic materials in a high-temperature hydrothermal environment is severely limited, particularly for some catalytic reaction systems such as catalytic cracking and the like with high temperature and water or steam. Therefore, how to improve the hydrothermal stability of the catalytic material while maintaining high activity has become one of the hot spots of attention.
CN108163869A discloses a method for improving the hydrothermal stability of a silicon-based mesoporous material, which comprises placing the silicon-based mesoporous material and ionic liquid in a closed reaction kettle, heating and insulating the reaction kettle, filtering, drying, and finally roasting at high temperature. According to the method, the silicon-based mesoporous material is subjected to high-temperature secondary treatment by adopting the environment-friendly ionic liquid, and the dehydration condensation effect of the ionic liquid on the silicon hydroxyl on the surface of the pore wall of the silicon-based mesoporous material under the high-temperature condition is utilized, so that the crosslinking degree of the pore wall is improved, the structural stability of the material is improved, and the aim of improving the hydrothermal stability of the silicon-based mesoporous material is fulfilled. After the SBA series silicon-based mesoporous materials treated by the method are treated by 100 percent of water vapor at 900 ℃ for 17 hours, the materials can still keep good ordered mesoporous structures,
CN109650422A discloses a method for improving hydrothermal stability of a mesoporous alumina material, which comprises the steps of mixing and stirring a triblock polymer template agent, an aluminum source, an inorganic acid and a solvent according to a certain mass ratio for reaction, standing the obtained slurry for 12-48 h, mixing the obtained solid and an ionic liquid according to the ionic liquid, and placing the mixture in a closed reaction kettle for treatment at 80-180 ℃. Then filtering and drying, and finally roasting at high temperature to obtain the high hydrothermal stability mesoporous alumina material.
CN110817885A discloses a method for improving the hydrothermal stability of a mesoporous silicon molecular sieve, which comprises loading a hydrothermal carbon layer on the surface of a mesoporous silicon molecular sieve by a hydrothermal carbonization method, and then improving the hydrothermal stability by high-temperature calcination. The method not only can obviously improve the hydrothermal stability of the mesoporous silicon molecular sieve, but also can well maintain the mesoporous structure of the molecular sieve. The hydrothermal carbonization method is characterized in that an aminated molecular sieve is used as a carrier, biomass is used as a carbon source, water is used as a reaction medium, and a hydrothermal carbon layer is loaded on the surface of a mesoporous silicon molecular sieve. The method is simple and convenient to operate, low in cost, wide in application range, easy to industrialize and wide in application prospect in the fields of catalysis and the like.
CN104891525A discloses a preparation method of a strong-acid high-stability mesoporous molecular sieve. The preparation method comprises the steps of firstly synthesizing a Y-shaped molecular sieve precursor, then assembling the Y-shaped molecular sieve precursor by adopting a crystal seed method under an acidic condition to obtain a first-step crystallization product, finally adjusting the pH value of the first-step crystallization product, and carrying out second-step crystallization to obtain a product. The mesoporous molecular sieve prepared by the invention shows excellent hydrothermal stability, after the hydrothermal treatment at 800 ℃ and 100% of water vapor, the specific surface area retention rate is more than 46%, and the mesoporous molecular sieve has better performance when being used as a component of a catalytic cracking catalyst for heavy oil.
In the above patents, the conventional methods for improving hydrothermal stability include methods such as high-temperature treatment with ionic liquid, carbon layer coating on the surface, aluminum atom doping, etc., and the hydrothermal stability can be remarkably improved by treating mesoporous silica, mesoporous alumina, and mesoporous and microporous molecular sieves. However, the activity of the catalyst is greatly reduced by the treatments of ionic liquid surface treatment, carbonization layer coverage, in-situ crystallization and the like, and how to improve the hydrothermal stability of the catalytic material on the premise of keeping high activity becomes a major technical problem to be solved at present.
Disclosure of Invention
The invention aims to overcome the defect that the high activity and the water-resistant thermal stability of the catalyst in the prior art cannot be considered at the same time, and provides the catalyst with high activity and water-resistant thermal stability and the preparation method thereof.
The high-activity hydrothermal-stability catalyst provided by the invention adopts surface covering, metal doping and rare earth modification methods to treat the precursor gel of the catalyst, so that the hydrothermal-stability of the catalyst is improved, and the metal active center of the catalyst is increased by using transition metal and rare earth metal.
The invention is realized by the following technical scheme:
a high-activity hydrothermal-stability-resistant catalyst is prepared by mixing high-activity hydrothermal-stability-resistant catalyst powder, a binder and a forming aid, preparing the mixture into a spherical or strip-shaped catalyst by a forming device, and drying and roasting the spherical or strip-shaped catalyst; the catalyst powder with high activity and hydrothermal stability comprises a covering component, a doping metal, a rare earth metal and a precursor, wherein the covering component accounts for 0.02-20 wt%, the doping metal accounts for 0.02-10 wt%, the rare earth metal accounts for 0.02-10 wt% and the precursor accounts for 60-99.4 wt% of the total solid content of the catalyst powder by mass percent;
the covering component is one or more of ethyl orthosilicate, silicon tetrachloride, titanium tetrachloride and n-butyl titanate;
the doped metal is one or more of manganese, tungsten, molybdenum, titanium, zirconium, germanium, tin and lead;
the rare earth metal is one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
the precursor is one or more of silicon-containing composite oxide, high-silicon molecular sieve, silicon dioxide, mesoporous silicon dioxide and mesoporous alumina;
the high-activity hydrothermal-stability-resistant catalyst powder is prepared by the following preparation steps:
1) surface covering: the precursor is prepared by a sol-gel method, the surface and pore channels of the precursor are covered by silicon/titanium at the gel stage of the precursor, namely, an alcohol solvent is used for replacing water in the hydrogel of the precursor, then the precursor is treated by the alcohol solvent containing a covering component, finally the alcohol solvent is replaced by the water and the covering component is catalyzed and hydrolyzed to obtain the precursor covered on the surface, wherein the alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol and ethylene glycol;
2) metal doping: adding soluble doped metal salt-inorganic acid solution into the precursor covered on the surface in the gel production process or the gel aging stage to bond the doped metal and the precursor skeleton silicon-aluminum, and washing with water to remove unreacted soluble doped metal salt and inorganic acid to obtain a metal doped precursor;
3) rare earth modification: introducing rare earth metal salt into the metal-doped precursor by an ion exchange method, an impregnation method or a coprecipitation method to obtain a rare earth modified precursor;
4) and drying, roasting and crushing the rare earth modified precursor to obtain the high-activity waterproof thermal stability catalyst powder.
In the technical scheme of the high-activity hydrothermal-stability-resistant catalyst, the silicon-containing composite oxide is one or more of a silicon-aluminum composite oxide, a silicon-magnesium composite oxide and a silicon-titanium composite oxide.
The high-silicon molecular sieve is SiO2/Al2O3High silicon Y molecular sieve SiO with mole ratio more than 5.02/Al2O3Beta molecular sieve or SiO with molar ratio more than 402/Al2O3One or more of ZSM-5 molecular sieves with the molar ratio of more than 60.
The mesoporous silica is one or more of MCM-41, SBA-15 and MCM-49.
The invention also provides a preparation method of the high-activity waterproof thermal stability catalyst, which comprises the following steps:
1) surface covering: firstly, covering the surface and pore channels of the precursor with silicon/titanium in a gelling stage, wherein the step comprises the steps of replacing water in the hydrogel of the precursor with an alcohol solvent, then treating the hydrogel with the alcohol solvent containing a covering component, finally replacing the alcohol solvent with water and catalyzing the hydrolysis of the covering component to obtain the precursor covered on the surface, wherein the alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol and ethylene glycol;
2) metal doping: adding a soluble doped metal salt-inorganic acid solution in the gel production process or the gel aging stage after the surface of the precursor is covered to enable the doped metal to be bonded with the precursor framework silicon-aluminum, and then washing with water to remove unreacted soluble doped metal salt and inorganic acid to obtain a metal doped precursor;
3) rare earth modification: introducing rare earth metal salt into a metal-doped precursor through an ion exchange method, an impregnation method and a coprecipitation method to obtain a rare earth modified precursor;
4) drying and roasting the rare earth modified precursor to obtain high-activity waterproof thermal stability catalyst powder;
5) mixing the high-activity water-resistant thermal-stability catalyst powder with a binder and a forming auxiliary agent, preparing the mixture into a spherical or strip-shaped catalyst by forming equipment, and drying and roasting the spherical or strip-shaped catalyst to obtain the high-activity water-resistant thermal-stability catalyst.
In the preparation method, the doping metal of the soluble doping metal salt-inorganic acid is preferably one or more of manganese, tungsten, molybdenum, titanium, zirconium, germanium, tin and lead;
the rare earth metal salt is one or more soluble metal salts of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
In the preparation method, the soluble doped metal salt-inorganic acid is preferably a dilute manganese nitrate sulfuric acid solution with the concentration of 0.15-0.25 mol/L.
In the preparation method, the rare earth metal salt is further preferably cerium nitrate, the roasting temperature is 350-700 ℃, and the roasting time is 4-24 hours.
The invention further provides application of the high-activity hydrothermal-stability-resistant catalyst in catalytic reaction under the condition of a high-temperature hydrothermal process at 500-850 ℃.
Further preferably, when the high-activity hydrothermal stability resistant catalyst is applied to a heavy oil catalytic cracking reaction under a high-temperature hydrothermal process condition, the heavy oil conversion rate is more than 80wt%, the low-carbon olefin selectivity is more than 80%, and the coke yield is less than 10 wt%.
The high-activity hydrothermal-resistant stable catalyst can be formed by spray drying, rolling ball forming, extrusion molding, powerful granulation and the like.
The high-activity water-resistant thermal-stability catalyst for the fluid catalytic cracking reaction is a microspherical catalyst, the particle size distribution is 20-200 mu m, the forming method is a spray drying method, the inlet temperature of a spray drying tower is 300-550 ℃, and the outlet temperature is 90-280 ℃.
The high-activity water-resistant thermal stability catalyst has higher pore wall thickness and better hydrothermal stability in a high-temperature hydrothermal environment. The catalyst also has framework-doped metal, and the metal framework doping and the framework elements such as silicon, aluminum and the like in the carrier form bonding, so that the doped metal can slow down the damage of water vapor to the framework elements under the high-temperature hydrothermal condition, can also generate defect sites, has catalytic activity, and further improves the hydrothermal stability and the catalytic activity of the catalyst. And finally, introducing rare earth metal to further protect doped metal and catalyst framework elements and improve the activity and stability of the catalyst again.
The surface and the pore channel of the catalyst carrier are covered by silicon/titanium, the wall thickness of the pore channel of the carrier is improved, the hydrothermal stability of the catalyst is improved, and the hydrothermal stability is further improved by doping a transition metal framework and loading rare earth metal. The catalyst powder is treated for a long time under the hydrothermal condition of 800 ℃, and the specific surface area is kept between 100 and 390m2G, high temperature hydrothermal stabilityIs excellent.
Compared with the existing catalyst, the high-activity water-resistant thermal-stability catalyst prepared by the invention has the following advantages:
(1) excellent high-temperature hydrothermal stability: the hydrothermal stability of the catalyst carrier is greatly improved through the wall thickness of the pore channel, the doping of the transition metal framework and the loading of the rare earth metal, the catalyst powder is treated for a long time under the hydrothermal condition of 800 ℃, and the specific surface area is up to 390m2The formed catalyst is treated for a long time under the hydrothermal condition of 800 ℃, and the specific surface area reaches up to 250m2/g
(2) High-activity catalytic performance: the catalyst is doped with a transition metal framework and rare earth metal, a defect center is generated by using the transition metal doped with the framework to form a high-activity catalytic center, the rare earth metal load further improves the activity and the stability of the catalyst, and the catalyst has higher activity in heavy oil conversion rate of more than 80wt% in a heavy oil catalytic cracking reaction under a high-temperature hydrothermal condition. The high-activity high-hydrothermal-stability catalyst is particularly suitable for heavy oil catalytic cracking reaction processes of residual oil, oil sand asphalt and the like in a high-temperature hydrothermal environment, and has the advantages of high heavy oil conversion rate of more than 80wt%, low-carbon olefin selectivity of more than 80%, coke yield of less than 10wt% and high activity and hydrothermal stability in the catalytic cracking reaction taking the residual oil as a raw material.
Detailed Description
The following describes in detail embodiments of the highly active water-resistant thermostable catalyst and the preparation method of the present invention by specific comparative examples and examples, but is not limited to the examples.
The invention adopts the methods of surface covering, metal doping and rare earth modification to treat the catalyst precursor gel, improves the water-proof thermal stability of the catalyst, utilizes transition metal and rare earth metal to increase the active center of the catalyst metal, and the methods of surface covering, metal doping and rare earth modification can be an impregnation method, a washing displacement method, an ion exchange method and a coprecipitation method, and can also be other metal loading and modification methods.
The inventor finds that the titanium/silicon covering component, the transition metal and the rare earth metal are screened, the carrier is subjected to silicon/titanium surface covering, transition metal framework doping and rare earth metal loading, the hydrothermal stability and activity of the catalyst can be effectively improved, the hydrothermal stability is high at 500-850 ℃, the catalyst is suitable for catalytic reaction under a high-temperature hydrothermal condition, and the catalyst is more suitable for catalytic cracking reaction of heavy oil such as residual oil, oil sand asphalt and the like.
The method for evaluating the performance of the high-activity water-resistant thermal stability catalyst comprises the following steps:
a fluidized bed pilot plant was used to evaluate the high activity hydrothermal stability catalyst, and the properties of the heavy oil feedstock used are shown in Table 1.
The catalyst for heavy oil catalytic cracking performance reaction is subjected to aging treatment for 24 hours at 800 ℃ in advance with 100% water vapor, samples before and after hydrothermal treatment are subjected to nitrogen adsorption to determine BET specific surface area and pore volume, and retention rates of the specific surface area and the pore volume after the hydrothermal treatment are calculated, and relevant data are shown in Table 2.
The performance evaluation of the high-activity hydrothermal stability catalyst is carried out in a fluidized bed pilot plant, and the process conditions are as follows: the reaction pressure is 0.2 MPa, the reaction temperature is 550 ℃, the weight ratio of steam to raw oil is 0.3:1, the agent-oil ratio is 12:1, and the contact time is 2 s. The gas phase product is collected and measured by refinery gas chromatography, the liquid product is distilled to measure the distillation range by adopting the real boiling point, the composition of the liquid product family is measured by adopting the combination of chromatography-mass spectrometry, and the analytical data of the products of each embodiment are shown in Table 3.
Wherein, the calculation formula of the heavy oil conversion rate is as follows:
heavy oil conversion =
The inventive process is illustrated below by way of example, but not by way of limitation.
Comparative example
(1) Selecting mesoporous silica hydrogel as a precursor, drying the precursor for 12 hours at 120 ℃, and crushing to obtain comparative catalyst powder: the BET specific surface area is 687m2Per g, pore volume 0.71cm3The mesoporous silicon dioxide powder is firstly subjected to hydrothermal aging treatment and then is aged by 100 percent of water vapor at 800 DEG CAfter 24 hours of treatment, the specific surface area and the pore volume of the catalyst after hydrothermal treatment are tested, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and relevant data are shown in a table 2.
(2) The mesoporous silica is crushed, kaolin, alumina sol and water are added, the mixture is stirred to prepare slurry, the solid content of the slurry is controlled within 20%, the slurry is stirred and beaten for 6 hours, the proportion of the mesoporous silica in the solid compound is 40wt%, the proportion of the kaolin is 40wt%, and the proportion of the alumina in the alumina sol is 20 wt%.
(3) And (3) spray-drying the pulped slurry into microspheres of 40-150 um, and controlling the inlet temperature of a spray-drying tower to be 450 ℃ and the outlet temperature to be 110 ℃.
(4) The microspherical catalyst obtained by spraying was dried at 120 ℃ for 12 hours and calcined at 650 ℃ for 4 hours to obtain a comparative catalyst.
(5) Catalyst evaluation and product analysis: the evaluation of the catalyst raw materials is that the specific analysis data are shown in table 1, the catalyst is aged for 24 hours at 800 ℃ and 100 percent water vapor in advance, and the high-temperature hydrothermal condition of an industrial device is simulated. After hydrothermal treatment, the catalyst reaction performance is evaluated on a fluidized bed pilot plant, and the process conditions are as follows: the reaction pressure is 0.2 MPa, the temperature is 550 ℃, the weight ratio of steam to raw oil is 0.3:1, the agent-oil ratio is 12:1, the contact time is 2s, the gas product is collected and measured by adopting refinery gas chromatography, the distillation range of the liquid product is measured by adopting real boiling point distillation, the composition of the liquid product family is measured by adopting chromatography-mass spectrometry, and the analytical data of the products of each embodiment are shown in Table 3.
Example 1
(1) The high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doped metal, a rare earth metal and a precursor, wherein the covering component is 0.77wt%, the doped metal is 0.86wt%, the rare earth metal is 0.25wt%, the rest components are precursors, and the precursors are mesoporous silicon dioxide.
(2) Covering the surface of the precursor: the method comprises the steps of adopting 1000g of mesoporous silica hydrogel (the mesoporous silica hydrogel is the same as a comparative example), wherein the solid content of silica in the gel is 15wt%, the rest components are water, firstly using an ethanol solvent to replace the water in the mesoporous silica gel, using the ethanol solvent with the concentration of n-butyl titanate of 0.1wt% to treat, consuming 5000g of the solvent, finally using water to replace the alcohol solvent and catalyzing the hydrolysis of the n-butyl titanate to obtain a precursor with a covered surface, wherein the mass of the covering component is 1.18g (calculated by the mass of titanium dioxide), and the mass of the precursor is 150g (calculated by the mass of silica).
(3) Doping transition metal: preparing a manganese nitrate dilute sulfuric acid solution, wherein the mass fraction of manganese nitrate is 0.25wt%, the pH value of the solution is 2, dipping the precursor covered on the surface in the step (2) by 2000g of the manganese nitrate dilute sulfuric acid solution, wherein the dipping temperature is 60 ℃, the dipping time is 12 hours, washing the precursor to be neutral by deionized water after dipping to obtain a transition metal doped precursor, and detecting that the mass of the transition metal doped manganese oxide is 1.31 g.
(4) Rare earth modification: preparing a rare earth modified precursor by using an ion exchange method, preparing 5000g of a cerium nitrate solution with the cerium nitrate concentration of 0.15wt%, contacting the cerium nitrate solution with the transition metal doped precursor obtained in the step (3) at 80 ℃, circulating the cerium nitrate solution for 12 hours, washing the cerium nitrate solution with deionized water to obtain the rare earth modified precursor, and detecting that the mass of the rare earth metal cerium oxide is 0.38 g.
(5) And (3) drying the rare earth modified precursor prepared in the step (4) at 120 ℃ for 12 hours, then roasting at 550 ℃ for 4 hours, and crushing to obtain the high-activity waterproof thermal stability catalyst powder. The powder is subjected to hydrothermal aging treatment under the same treatment conditions as the comparative examples, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and the related data are shown in Table 2.
(6) The spray forming of the catalyst is the same as the comparative example, and the drying and roasting conditions are the same as the comparative example.
(7) Catalyst evaluation and product analysis were the same as in the comparative example.
Example 2
(1) The high-silicon ZSM-5 molecular sieve hydrogel is selected, and the physical property of the molecular sieve is SiO2With Al2O3A molar ratio of 92, a sodium oxide content of 0.02% by weight and a BET specific surface area of 347m2G, pore volume 0.30cm3/g。
(2) The high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doped metal, a rare earth metal and a precursor, wherein the covering component is 1.01wt%, the doped metal is 0.76wt%, the rare earth metal is 0.28wt% and the rest components are the precursor in percentage by mass of the total solid content of the catalyst.
(3) Covering the surface of the precursor: the method comprises the steps of adopting 1000g of high-silicon ZSM-5 molecular sieve hydrogel, wherein the solid content of silicon dioxide in the gel is 22wt%, and the balance is water, firstly using an ethanol solvent to dissolve the water in the high-silicon ZSM-5 molecular sieve gel, using the ethanol solvent with the n-butyl titanate concentration of 0.2wt% to treat the gel, consuming 5000g of the solvent, finally using water to replace the alcohol solvent and catalyze the hydrolysis of the n-butyl titanate to obtain a precursor with a covered surface, and detecting that the mass of the covering component is 2.28g (calculated by the mass of titanium dioxide) and the mass of the precursor is 220g (calculated by the total mass of silicon dioxide and aluminum oxide).
(4) Doping transition metal: preparing a manganese nitrate dilute sulfuric acid solution, wherein the mass fraction of manganese nitrate is 0.35wt%, the pH value of the solution is 3.5, dipping the precursor covered on the surface in the step (3) by 2000g of the manganese nitrate dilute sulfuric acid solution, wherein the dipping temperature is 60 ℃, the dipping time is 12 hours, washing the precursor to be neutral by deionized water after dipping to obtain a transition metal doped precursor, and detecting that the mass of the transition metal doped manganese oxide is 1.72 g.
(5) Rare earth modification: preparing a rare earth modified precursor by using an ion exchange method, preparing 5000g of a cerium nitrate solution with the cerium nitrate concentration of 0.15wt%, contacting the cerium nitrate solution with the transition metal doped precursor obtained in the step (4) at 80 ℃, circulating the cerium nitrate solution for 12 hours, washing the cerium nitrate solution with deionized water to obtain the rare earth modified precursor, and detecting that the mass of the rare earth metal cerium oxide is 0.64 g.
(6) And (3) drying the rare earth modified precursor prepared in the step (5) at 120 ℃ for 12 hours, then roasting at 550 ℃ for 4 hours, and crushing to obtain the high-activity waterproof thermal stability catalyst powder. The powder is subjected to hydrothermal aging treatment under the same treatment conditions as the comparative examples, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and the related data are shown in Table 2.
(7) The spray forming of the catalyst is the same as the comparative example, and the drying and roasting conditions are the same as the comparative example.
(8) Catalyst evaluation and product analysis were the same as in the comparative example.
Example 3
(1) Selecting silicon-aluminum composite oxide hydrogel, wherein the physical property of the silicon-aluminum composite oxide is SiO284.15wt% of Al2O315.62wt%, 0.23wt% of sodium oxide, and a BET specific surface area of 315m2Per g, pore volume 0.57cm3/g。
(2) The high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doped metal, a rare earth metal and a precursor, wherein the covering component accounts for 1.59wt%, the doped metal accounts for 0.91wt%, the rare earth metal accounts for 0.40wt% and the rest components are the precursor in percentage by mass of the total solid content of the catalyst.
(3) Covering the surface of the precursor: 1000g of silicon-aluminum composite oxide hydrogel is adopted, the solid content of silicon dioxide in the hydrogel is 18wt%, the balance is water, an ethanol solvent is used for replacing water in the silicon-aluminum composite oxide hydrogel, the ethanol solvent with the concentration of n-butyl titanate of 0.25wt% is used for processing, 5000g of the solvent is consumed, finally the alcohol solvent is replaced by water, the hydrolysis of the n-butyl titanate is catalyzed, a precursor with a covered surface is obtained, the mass of the covering component is detected to be 2.86g (calculated by the mass of titanium dioxide), and the mass of the precursor is 180g (calculated by the mass of silicon dioxide and aluminum oxide).
(4) Doping transition metal: preparing a manganese nitrate dilute sulfuric acid solution, wherein the mass fraction of manganese nitrate is 0.32wt%, the pH value of the solution is 2, dipping the precursor covered on the surface in the step (3) by 2000g of the manganese nitrate dilute sulfuric acid solution, wherein the dipping temperature is 60 ℃, the dipping time is 12 hours, washing the precursor to be neutral by deionized water after dipping to obtain a transition metal doped precursor, and detecting that the mass of the transition metal doped manganese oxide is 1.68 g.
(5) Rare earth modification: preparing a rare earth modified precursor by using an ion exchange method, preparing 5000g of a cerium nitrate solution with the cerium nitrate concentration of 0.20wt%, contacting the cerium nitrate solution with the transition metal doped precursor obtained in the step (4) at 80 ℃, circulating the cerium nitrate solution for 12 hours, washing the cerium nitrate solution with deionized water to obtain the rare earth modified precursor, and detecting that the mass of the rare earth metal cerium oxide is 0.72 g.
(6) And (3) drying the rare earth modified precursor prepared in the step (5) at 120 ℃ for 12 hours, then roasting at 550 ℃ for 4 hours, and crushing to obtain the high-activity waterproof thermal stability catalyst powder. The powder is subjected to hydrothermal aging treatment under the same treatment conditions as the comparative examples, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and the related data are shown in Table 2.
(7) The spray forming of the catalyst is the same as the comparative example, and the drying and roasting conditions are the same as the comparative example.
(8) Catalyst evaluation and product analysis were the same as in the comparative example.
Example 4
(1) Silicon dioxide is selected as a precursor, SiO299.8wt% of sodium oxide, 0.2wt% of sodium oxide and 663m of BET specific surface area2G, pore volume 0.74cm3/g。
(2) The high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doping metal, a rare earth metal and a precursor, wherein the covering component is 2.34wt%, the doping metal is 0.84wt%, the rare earth metal is 0.33wt% and the rest components are the precursor in percentage by mass of the total solid content of the catalyst.
(3) Covering the surface of the precursor: the method comprises the steps of adopting 1000g of silicon dioxide hydrogel, wherein the solid content of silicon dioxide in the gel is 17wt%, and the balance is water, firstly using an ethanol solvent to replace the water in the silicon dioxide gel, treating the silicon dioxide gel with the ethanol solvent with the concentration of n-butyl titanate of 0.35wt%, consuming 5000g of the solvent, finally using water to replace the alcohol solvent and catalyzing the hydrolysis of the n-butyl titanate to obtain a precursor with a covered surface, and detecting that the mass of a covering component is 4.08g (calculated by the mass of titanium dioxide), and the mass of the precursor is 170g (calculated by the mass of silicon dioxide and aluminum oxide).
(4) Doping transition metal: preparing a manganese nitrate dilute sulfuric acid solution, wherein the mass fraction of manganese nitrate is 0.26wt%, the pH value of the solution is 2.5, dipping the precursor covered on the surface in the step (3) by 2000g of the manganese nitrate dilute sulfuric acid solution, wherein the dipping temperature is 60 ℃, the dipping time is 12 hours, washing the precursor to be neutral by deionized water after dipping to obtain a transition metal doped precursor, and detecting that the mass of the transition metal doped manganese oxide is 1.48 g.
(5) Rare earth modification: preparing a rare earth modified precursor by using an ion exchange method, preparing 5000g of a cerium nitrate solution with the concentration of 0.25wt%, contacting the cerium nitrate solution with the transition metal doped precursor obtained in the step (4) at 80 ℃, circulating the cerium nitrate solution for 12 hours, washing the cerium nitrate solution with deionized water to obtain the rare earth modified precursor, and detecting that the mass of the rare earth metal cerium oxide is 0.58 g.
(6) And (3) drying the rare earth modified precursor prepared in the step (5) at 120 ℃ for 12 hours, then roasting at 550 ℃ for 4 hours, and crushing to obtain the high-activity waterproof thermal stability catalyst powder. The powder is subjected to hydrothermal aging treatment under the same treatment conditions as the comparative examples, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and the related data are shown in Table 2.
(7) The spray forming of the catalyst is the same as the comparative example, and the drying and roasting conditions are the same as the comparative example.
(8) Catalyst evaluation and product analysis were the same as in the comparative example.
Example 5
(1) The precursor was selected as in example 2.
(2) The high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doped metal, a rare earth metal and a precursor, wherein the covering component is 1.01wt%, the doped metal is 0.61wt%, the rare earth metal is 0.28wt% and the rest components are the precursor in percentage by mass of the total solid content of the catalyst.
(3) The precursor surface coverage was the same as in example 2.
(4) Doping transition metal: preparing a molybdenum nitrate dilute sulfuric acid solution, wherein the mass fraction of manganese nitrate is 0.26wt%, the pH value of the solution is 2.5, dipping the precursor covered on the surface in the step (3) by 2000g of the manganese nitrate dilute sulfuric acid solution, wherein the dipping temperature is 60 ℃, the dipping time is 12 hours, washing the precursor to be neutral by deionized water after dipping to obtain a transition metal doped precursor, and detecting that the mass of the transition metal doped manganese oxide is 1.36 g.
(5) The rare earth modification was the same as in example 2.
(6) And (3) drying the rare earth modified precursor prepared in the step (5) at 120 ℃ for 12 hours, then roasting at 550 ℃ for 4 hours, and crushing to obtain the high-activity waterproof thermal stability catalyst powder. The powder is subjected to hydrothermal aging treatment under the same treatment conditions as the comparative examples, and the specific surface area and the pore volume retention rate after hydrothermal treatment are calculated, and the related data are shown in Table 2.
(7) The spray forming of the catalyst is the same as the comparative example, and the drying and roasting conditions are the same as the comparative example.
(8) Catalyst evaluation and product analysis were the same as in the comparative example.
TABLE 1 basic Properties of the raw materials used in the examples
TABLE 2 BET data before and after hydrothermal treatment of the catalyst
| Analysis item | Comparative example | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Specific surface area before hydrothermal treatment, m2/g | 687 | 687 | 347 | 315 | 663 | 347 |
| Pore volume, cm, before hydrothermal treatment3/g | 0.71 | 0.71 | 0.3 | 0.57 | 0.74 | 0.3 |
| Specific surface area after hydrothermal treatment, m2/g | 124 | 386 | 256 | 240 | 390 | 267 |
| Pore volume, cm after hydrothermal treatment3/g | 0.15 | 0.47 | 0.25 | 0.43 | 0.5 | 0.26 |
| Specific surface area Retention% | 18.05 | 56.19 | 73.78 | 76.19 | 58.82 | 76.95 |
| Pore volume retention% | 21.13 | 66.20 | 83.33 | 75.44 | 67.57 | 86.67 |
Table 3 evaluation data table of catalyst performance
| Product analysis project | Comparative example | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Dry gas | 1.21 | 5.91 | 4.24 | 4.32 | 4.76 | 4.98 |
| Total liquefied gas | 12.68 | 23.12 | 24.95 | 25.18 | 20.02 | 25.29 |
| Low carbon olefin selectivity of liquefied gas% | 55.62 | 83.65 | 82.90 | 84.27 | 83.49 | 82.11 |
| Gasoline fraction wt% | 12.95 | 22.51 | 23.53 | 24.91 | 25.08 | 21.83 |
| Diesel fraction, wt.% | 17.53 | 27.54 | 24.12 | 22.37 | 25.94 | 25.99 |
| Wax oil fraction, wt.% | 21.21 | 10.11 | 12.68 | 12.93 | 13.33 | 10.41 |
| Oil slurry wt% | 15.57 | 1.73 | 1.80 | 1.37 | 1.96 | 1.58 |
| Coke, wt% | 18.85 | 9.08 | 8.68 | 8.92 | 8.91 | 9.92 |
| Heavy oil conversion rate,% | 63.22 | 88.16 | 85.52 | 85.7 | 84.71 | 88.01 |
Claims (8)
1. A high-activity hydrothermal-stability-resistant catalyst is characterized in that a spherical or bar-shaped catalyst is prepared by mixing high-activity hydrothermal-stability-resistant catalyst powder, a binder and a forming auxiliary agent through a forming device, and then drying and roasting the mixture;
the high-activity hydrothermal-stability-resistant catalyst powder consists of a covering component, a doping metal, a rare earth metal and a precursor, and the mass percentage of each component is as follows: 0.02-20 wt% of covering component, 0.02-10 wt% of doping metal, 0.02-10 wt% of rare earth metal and 60-99.4 wt% of precursor;
the covering component is one or more of ethyl orthosilicate, silicon tetrachloride, titanium tetrachloride and n-butyl titanate;
the doped metal is one or more of manganese, tungsten, molybdenum and zirconium;
the rare earth metal is one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
the precursor is one or more of silicon-containing composite oxide, high-silicon molecular sieve, silicon dioxide, mesoporous silicon dioxide and mesoporous alumina; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-magnesium composite oxide and silicon-titanium composite oxide;
the high-activity hydrothermal-stability-resistant catalyst powder is prepared by the following preparation steps:
1) surface covering: the precursor is prepared by a sol-gel method, water in the hydrogel of the precursor is replaced by an alcohol solvent in a gel stage, then the hydrogel is treated by the alcohol solvent containing a covering component, and finally the alcohol solvent is replaced by the water and the covering component is catalyzed to hydrolyze to obtain the precursor with a covered surface, wherein the alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol and glycol;
2) metal doping: adding soluble doped metal salt-inorganic acid solution into the precursor covered on the surface in the gel production process or the gel aging stage to bond the doped metal and the precursor skeleton silicon-aluminum, and washing with water to remove unreacted soluble doped metal salt and inorganic acid to obtain a metal doped precursor;
3) rare earth modification: introducing rare earth metal salt into the metal-doped precursor by an ion exchange method, an impregnation method or a coprecipitation method to obtain a rare earth modified precursor;
4) and drying, roasting and crushing the rare earth modified precursor to obtain the high-activity waterproof thermal stability catalyst powder.
2. The catalyst of claim 1, wherein the high-silicon molecular sieve is SiO2/Al2O3High silicon Y molecular sieve SiO with mole ratio more than 5.02/Al2O3Beta molecular sieve or SiO with molar ratio more than 402/Al2O3One or more of ZSM-5 molecular sieves with the molar ratio of more than 60.
3. The catalyst with high activity and hydrothermal stability as claimed in claim 1, wherein the mesoporous silica is one or more selected from MCM-41, SBA-15 and MCM-49.
4. A method for preparing the high-activity water-resistant thermostable catalyst according to claim 1, characterized by comprising the steps of:
1) surface covering: the precursor is firstly replaced with an alcohol solvent for water in the precursor hydrogel in the gelation stage, then is treated with the alcohol solvent containing a covering component, and finally is replaced with the alcohol solvent and is hydrolyzed by catalyzing the covering component to obtain the precursor with a covered surface, wherein the alcohol solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol and ethylene glycol;
2) metal doping: adding a soluble doped metal salt-inorganic acid solution into the precursor after the surface is covered in the gel production process or the gel aging stage to bond the doped metal and the precursor skeleton silicon-aluminum, and washing with water to remove unreacted soluble doped metal salt and inorganic acid to obtain a metal doped precursor;
3) rare earth modification: introducing rare earth metal salt into a metal-doped precursor through an ion exchange method, an impregnation method and a coprecipitation method to obtain a rare earth modified precursor;
4) drying and roasting the rare earth modified precursor to obtain high-activity waterproof thermal stability catalyst powder;
5) mixing the high-activity water-resistant thermal-stability catalyst powder with a binder and a forming auxiliary agent, preparing the mixture into a spherical or strip-shaped catalyst by forming equipment, and drying and roasting the spherical or strip-shaped catalyst to obtain the high-activity water-resistant thermal-stability catalyst.
5. The preparation method of the high-activity water-resistant thermal-stability catalyst according to claim 4, wherein the soluble doped metal salt-inorganic acid is a dilute manganese nitrate sulfuric acid solution with a concentration of 0.15-0.25 mol/L.
6. The preparation method of the high-activity water-resistant thermostable catalyst according to claim 4, wherein the rare earth metal salt is cerium nitrate, the calcination is performed at 350 to 700 ℃ for 4 to 24 hours.
7. The application of the high-activity water-resistant thermal-stability catalyst of claim 1 in catalytic reaction under the condition of a high-temperature hydrothermal process at 500-850 ℃.
8. The use of claim 7, wherein the catalytic reaction is heavy oil catalytic cracking, and the heavy oil conversion is greater than 80wt%, the low carbon olefin selectivity is greater than 80wt%, and the coke yield is less than 10 wt%.
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