CN1253859A - 一种生产中间馏分油的加氢裂化催化剂及其制备 - Google Patents
一种生产中间馏分油的加氢裂化催化剂及其制备 Download PDFInfo
- Publication number
- CN1253859A CN1253859A CN98114459A CN98114459A CN1253859A CN 1253859 A CN1253859 A CN 1253859A CN 98114459 A CN98114459 A CN 98114459A CN 98114459 A CN98114459 A CN 98114459A CN 1253859 A CN1253859 A CN 1253859A
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- Prior art keywords
- catalyst
- zeolite
- pore volume
- content
- amorphous aluminum
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 75
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010457 zeolite Substances 0.000 claims abstract description 75
- 239000011148 porous material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract 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 abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 44
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000011959 amorphous silica alumina Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
- 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 9
- 239000012065 filter cake Substances 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000002101 lytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 102100030310 5,6-dihydroxyindole-2-carboxylic acid oxidase Human genes 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 101000773083 Homo sapiens 5,6-dihydroxyindole-2-carboxylic acid oxidase Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- ZRKLEAHGBNDKHM-UHFFFAOYSA-N N,n'-diallyl-2,3-dihydroxysuccinamide Chemical compound C=CCNC(=O)C(O)C(O)C(=O)NCC=C ZRKLEAHGBNDKHM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Classifications
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- 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
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
一种中油型加氢裂化催化剂,其组成为一种改性超疏水Y沸石5—40w%,无定形硅铝10—50w%,氧化铝15—30w%,ⅥB族金属氧化物10—40w%,Ⅷ金属氧化物1—10w%。所含的Y沸石SiO2/Al2O3摩尔比5—25,红外酸度0.2—0.6mmol/g在25℃,P/Po为0.1条件下,水吸附量小于5w%。所含的无定形硅铝SiO2含量15—50w%,比表面300—600m2/g,孔容0.8—1.5ml/g,红外酸度0.25—0.60mmol/g。本发明催化剂有较高的活性和中油选择性,可用于多生产中间馏分的加氢裂化过程。
Description
本发明涉及一种加氢裂化催化剂及其制备方法,特别是用于处理石油烃物料,生产中间馏分油的催化剂及其制备。
目前世界各炼油厂都面临着原料越来越重、质量越来越差的问题,加氢裂化过程已成为重质油轻质化的重要手段之一。加氢裂化催化剂是一种双功能催化剂,具有加氢性能和裂解性能,非贵金属加氢裂化催化剂一般选用VIB和VIII族金属作加氢组份,酸性组分可选用晶型沸石和/或无定形硅铝。单纯用无定形硅铝作酸性组分的无定形加氢裂化催化剂,虽然选择性较高,但活性低,操作上的灵活性受到限制,而沸石在加氢裂化催化剂中的使用是加氢裂化技术的一次质的飞跃,它改变了以往以无定形硅铝为活性组分的加氢裂化催化剂活性低、运转周期短的缺点,使催化剂反应温度大为降低。特别地,为了增加催化剂的操作灵活性,以适应处理市场上所面临的日益变差的原料,目前工业上普遍使用的中油型加氢裂化催化剂都需要无定形硅铝与沸石组分配合使用,以满足对催化剂活性和中油选择性的双重需要。
对于中油型加氢裂化催化剂,除了考虑活性外,特别需要考虑中油选择性。沸石相对酸性硅铝的较强的酸性中心固然可以增加催化剂的裂解活性,但其强烈的裂解能力会导致中油选择性的大幅下降,因此需要在活性和中油选择性这一对矛盾中寻找到一种更好的均衡。要解决反应的活性与选择性这一对矛盾,必须按照中油型加氢裂化催化剂对酸性裂解功能和加氢功能平衡匹配的要求,开发新型的沸石及无定形硅铝材料,并通过调整无定形硅铝与沸石组分在载体中适宜的比例,来达到反应过程中所需的活性和选择性的最佳位置,从而达到我们最终的目的。
US4894142公开了一种加氢裂化催化剂,目的在于提高催化剂的中油选择性,该催化剂是含有无定形硅铝和一种低酸度Y型沸石,该催化剂所涉及的沸石特点在于其TPD酸度小于2.0mmol/g,最好1.5mmol/g,为了降低酸度,该专利涉及的沸石的主要制备特点是在高温下热处理原料沸石,包括676-788℃下水热处理或最好704℃的通入惰性气体的干式热处理,由于该沸石酸度过低,用于催化剂组分处理原料油时,尽管转化率85w%,反应温度却高达410℃以上,由于反应温度高,抑制了加氢反应,沸石的热裂化性能趋势增强,使催化剂的中油选择性提高不明显,中油选择性不超过70%,在活性和中油选择性这一对矛盾解决上不能说寻找到了一种更好的均衡。
US4517074专利公开了一种加氢裂化催化剂,生产300-700°F(149-371℃)的中间馏分油,进料最好是加氢脱氮和/或加氢脱硫进料,该催化剂除了使用沸石组分外,其特点在于使用一种Al2O3-SiO2分散体系,其SiO2含量达到20-65%,分散体系中的无定形硅铝虽然具有一定的裂解活性,但需要分散在氧化铝基体上如大孔γ-Al2O3作载体组分,以获得承载大量的加氢金属组分的孔容和比表面。该催化剂虽然有较高的中油选择性,一般80%以上,但活性较低,要达到60v%转化,反应温度一般在400℃以上,该专利实例通过使用一种在专利范围内的在γ-Al2O3分散有75%高硅铝的组分并配合沸石如LZ-10沸石,反应温度也仅达到389℃。
本发明的目的在于给出一种加氢裂化催化剂及其制备方法,用于加氢裂化过程处理重质烃物料以生产中间馏分油,具有活性好、中油选择性高的特点。本发明的目的还在于,给出一种超疏水Y沸石及一种无定形硅铝的制备方法,并使用这些组分来制备一种新型的中油型加氢裂化催化剂。
本发明催化剂组成为超疏水Y沸石5-40w%,无定形硅铝10-50w%,氧化铝粘合剂15-30w%,活性金属选自VIB族的Mo、W和/或VIII族的Co、Ni,VIB金属氧化物在催化剂中含10-40w%,VIII金属氧化物在催化剂中含1-10w%。本发明催化剂所涉及的超疏水Y沸石的SiO2/Al2O3摩尔比5-25,红外酸度0.2-0.6mmol/g,在25℃,P/Po为0.1条件下,水吸附量小于5w%;所涉及的无定形硅铝的SiO2含量15-50w%,比表面300-600m2/g,孔容0.8-1.5ml/g,红外酸度0.25-0.60mmol/g。
本发明催化剂的比表面为180-300m2/g,最好为200-250m2/g,孔容为0.25-0.45ml/g,最好为0.3-0.4ml/g,红外酸度为0.25-0.55mmol/g,最好为0.35-0.45mmol/g,4-15nm孔分布占总孔容的60-90%,最好为70-90%。
本发明催化剂所涉及的超疏水Y沸石的SiO2/Al2O3摩尔比最好为6.0-17;该沸石具有较高的结晶度,一般在75%-100%;非骨架铝占总铝量的10-50w%,比例适当;晶胞常数固定在一个极窄的范围内,一般在2.420~2.445nm,最好在2.425~2.435nm;具有明显的二次孔,即经改性处理后沸石中孔增加,并伴随着比表面、孔容的增加,比表面600-850m2/g,最好700-800m2/g;孔容0.2-0.6ml/g,最好0.3-0.5ml/g;大于2nm的二次孔占总孔容的50%以上;红外酸度最好为0.3-0.5mmol/g,并且强酸中心少,>450℃脱附的强酸中心少于25%。
本发明所涉及的无定形硅铝的最佳性质为:SiO2含量为20-40w%,比表面积为350-550m2/g,最好为400-500m2/g,孔容为0.9-1.4ml/g,最好为1.0-1.3ml/g,红外酸度为0.3-0.55mmol/g,最好为0.35-0.50mmol/g。
本发明催化剂最佳组成为超疏水Y沸石10-30w%,无定形硅铝20-40w%,粘合剂(干基氧化铝计)15-30w%,VIB族金属氧化物含量15-30w%,VIII族金属氧化物含量4-8w%。
本发明催化剂制备过程是将本发明催化剂所涉及的无定形硅铝10-50w%与5-40w%超疏水Y沸石组分混合均匀后,加入经硝酸胶溶的比表面积为240-280m2/g、孔容为0.4-0.5ml/g的小孔氧化铝粘合剂15-30w%混捏、碾压成团后,在挤条机上挤条成型而获得载体,再以常规的浸渍法等承载加氢活性金属获得本发明催化剂。
成型的载体条可以为园柱条,直径1.2-1.8mm,也可采用异形条如三叶草或四叶草形,经干燥、焙烧活化后得到载体,干燥温度在90-160℃,最好110-140℃,时间为6-12小时,最好8-10小时。焙烧活化温度在400-650℃,最好450-600℃,时间为1-10小时,最好3-6小时。
本发明催化剂所涉及的超疏水Y沸石制备步骤如下:
(1)制备Na2O含量小于0.2w%的Y沸石I。
(2)将Y沸石产物I置于高温焙烧炉中,在自身水蒸气或通入水蒸气,450℃-700℃,0.01-1.0MPa压力水蒸气下焙烧0.5-10小时,制得SiO2/Al2O3摩尔比为5.2-6.0的超疏水Y分子筛II。
上步骤得到的超疏水Y分子筛可以进一步用化学方法选择性地脱铝,可得SiO2/Al2O3摩尔比为6.5-25的超疏水Y分子筛。化学方法选择脱铝是用酸溶液(盐酸、硝酸、醋酸、草酸等)或有机络合剂(如乙酰丙酮、乙二胺四乙酸等)选择性地脱除沸石的非骨架铝。
其中Na2O含量小于0.2w%的Y沸石可用下面的a或b方法制备。
a、以NaY沸石为原料,用浓度为1.0-5.0M,最好是2.0-3.0M的铵盐溶液为交换液,沸石在交换浆液中浓度为0.05-1.0g/ml,最好是0.1-0.5g/ml,在70-150℃,最好是80-120℃下搅拌0.5-3小时,重复上述离子交换多次,直到制得Na2O<0.2w%的Y沸石。
b、以NaY沸石为原料,用同a中的离子交换方法离子交换2-3次,制得Na2O含量小于3.0w%的Y沸石产物I,然后在450~600℃,0.01~0.2MPa压力水蒸汽下处理0.5~3小时。然后用同a中的离子交换方法进行离子交换2~3次,得到Na2O<0.2w%的Y沸石。
本发明无定形硅铝是按以下过程制备的:
(a)将一种酸性铝盐溶液与一种碱性沉淀剂并流加入到有少量去离子水的反应容器中,在pH值6.0-10.0,温度50-70℃形成溶胶,中和反应时间为0.5-2小时;
(b)将(a)在pH8-9的条件下稳定0-60分钟;
(c)在5-10分钟内将一种硅化合物加入到(b)中;
(d)在pH值7.5-9.5,50-70℃下老化(c)10-60分钟;
(e)过滤并洗涤(d);
(f)将(e)于90-120℃下干燥粉碎而获得产品。上述(c)中所述的硅化合物可以是工业级的水玻璃或硅溶胶及其它硅化物。
本发明催化剂所涉及的Y沸石改性后,沸石硅铝分子比提高,固体酸量进一步降低。本发明催化剂所涉及的Y沸石经深度脱铝后,酸中心数降低,红外酸度降低到0.2-0.6mmol/g,最好0.3-0.5mmol/g。与现有技术制备的Y沸石相比,本发明催化剂所涉及的沸石具有较高的结晶度、比表面,并形成较多的弱酸及中强酸中心,其>450℃脱附的强酸中心一般不到25%,大部分集中在160-450℃脱附的弱及中强酸中心,因此保证不致过度裂解,但一定量的强酸中心也保证了催化剂的裂解活性。本发明催化剂所涉及的沸石改性后的孔性质,包括高比表面及较多的二次孔也促进了加氢活性的发挥,这有助于对多环芳烃或含氮杂环的开环活性的提高,并可提供更多的有效反应空间,满足需要有中等裂解活性和高加氢活性的中油型加氢裂化催化剂对重质烃物料裂解的要求。
现有技术的无定形硅铝比表面和孔容都较小,比表面都不超过300m2/g,一般需要和γ-Al2O3配合作为催化剂的载体以承载大量金属组分。本发明催化剂所涉及的无定形硅铝制备特点避免了在结晶化趋势下造成的孔结构的不理想,保证硅和铝原子有效地相互作用以产生酸性中心的前提下具有高比表面及大孔容,该无定形硅铝孔容可达0.8-1.5ml/g,在一个很宽的高硅含量范围内,仍可以得到高比表面大孔容无定形硅铝,如SiO2含量在45%时,比表面仍能达到450-550m2/g。大的比表面积可以承载大量加氢金属组分,酸性中心可以提供一定的裂解活性。大的孔容有利于反应物及生成物的进出,减少二次裂解发生的机会,减少积炭以延长催化剂的使用寿命。
本发明的加氢裂化催化剂以上述的超疏水Y沸石作为主要酸性组分,该沸石的酸性特点可以提供催化剂较缓和的裂解性能;沸石的高比表面二次孔结构可以促进加氢金属的分散,有利于加氢活性的发挥,并改善催化剂的孔分布以利于馏分油的裂化。另外,该催化剂以本发明所涉及的无定形硅铝为辅助酸性组分及主要载体组分,该无定形硅铝具有双功能,用于提供部分酸性裂解功能并作为承载加氢金属的主要载体组分,其适中的酸度和酸强度可以配合沸石提供较缓和的裂解性,同时高比表面和大孔容可以承载高量的加氢金属并促进金属的分散,并有利于反应物与生成物的进出,减少了二次或过度裂解发生的概率。因此,与以现有技术制备的中油型加氢裂化催化剂相比,本发明中油型加氢裂化催化剂具有高活性和明显的高中油选择性的特点。与参比催化剂相比,本发明催化剂同样条件下处理同样一种减压瓦斯油,表现出更好的活性或中油选择性。
本发明催化剂制备过程简单、方便,易于操作,适合工业上的生产。本发明催化剂用于加氢裂化过程,以生产中间馏分油。本发明催化剂特别适于处理重质烃物料,重质烃物料的馏程范围在250-600℃,一般在300-550℃,具有上述特点的原料油如瓦斯油、减压馏分油、脱沥清油、催化裂化循环油、页岩油、煤焦油等。反应条件一般在氢气存在条件下,反应压力5-30MPa,氢油比100-5000,空速0.1-5.0h-1,反应温度340-420℃。本发明催化剂在处理通常的VGO时,反应条件一般在氢气存在条件下,反应压力最好10-20MPa,氢油比500-2000,空速0.5-1.5h-1,反应温度370-410℃。
以下通过实施例进一步说明本发明所涉及的超疏水Y沸石、无定形硅铝及催化剂的制备方法及其性质和效果。
实例1
(1)1M3内衬搪瓷的交换罐中加入130kg业NH4NO3(大连化工厂产品,纯度>99.5%),加入800升工业净水,配成2M NH4NO3溶液,加热到70℃,加入120KgNaY沸石(温州催化剂厂产品,干基50w%),在70℃下搅拌交换3小时,重复此交换步骤12次,过滤,并水洗至中性,得到Na2O含量为0.18%的Y沸石,烘干。(2)将上述水洗烘干的沸石放入高压旋转炉中,快速升温至650℃,在0.4MPa压力100%水蒸气下焙烧6小时,得到本发明催化剂所涉及的超疏水Y沸石A。其物化性质见表1。
实例2
(1)取5.0kg NaY沸石(同实例1)加到50升浓度为2M的NH4NO3溶液中,在100℃下搅拌,离子交换2小时,共交换二次,然后过滤、洗涤至中性,并烘干,得到产物I。(2)将产物I置于高压旋转炉中,在550℃,100%水蒸气0.1MPa压力下焙烧2小时,得到产物II。(3)将产物II放入50升浓度为2M的NH4NO3溶液中,在100℃下搅拌离子交换2小时,共交换3次,然后过滤、洗涤至中性,并烘干,得到产物III。(4)将产物III置于高压旋转炉中,在550℃,100%水蒸气0.2MPa压力下焙烧4小时,得到本发明催化剂所涉及的超疏水Y沸石B。其物化性质见表1。
实例3
(1)将2.0kg NaY沸石(同实例2)加到160升浓度为3M的NH4NO3溶液中,在150℃下搅拌离子交换0.5小时,共离子交换12次,得到Na2O含量为0.17%的Y沸石,烘干,得到产物I。(2)将产物I放入高压旋转炉中,在700℃,0.01MPa压力、100%水蒸气下焙烧4小时,得到产物II。(3)取产物II400g,放入浓度为0.4M的4升盐酸溶液中,处理2小时,过滤、洗涤至中性,烘干,得到本发明催化剂所涉及的超疏水Y沸石C。其物化性质见表1。
实例4:
将实例1得到的超疏水Y沸石A100克;放入浓度为0.4M的1升乙酰丙酮溶液中,处理2小时,过滤,用3升去离子水洗涤,烘干,得到本发明超疏水Y沸石D。其物化性质见表。
表1超疏水Y沸石A-E的物化性质
实例 | 1 | 2 | 3 | 4 |
沸石编号 | A | B | C | D |
非骨架铝/总铝×100% | 45 | 40 | 35 | 10 |
二次孔(>2.0nm)% | 50 | 52 | 56 | 54 |
红外酸度(mmol/g) | 0.22 | 0.33 | 0.55 | 0.30 |
Na2O w% | 0.15 | 0.14 | 0.10 | 0.11 |
比表面(BET法)m2/g | 630 | 660 | 780 | 840 |
SiO2/Al2O3(摩尔比) | 5.2 | 6.0 | 13.0 | 23.9 |
晶胞常数,nm | 2.430 | 2.432 | 2.428 | 2.430 |
离子交换容量 | 0.051 | 0.045 | 0.057 | 0.053 |
正丁醇吸附残余值 | 0.22 | 0.25 | 0.15 | 0.17 |
水吸附量,25℃P/P0=0.1w% | 4.3 | 2.1 | 4.0 | 4.5 |
实例5
将3.2升一种工业级硫酸铝浓溶液加入到4.2升蒸馏水中,同时加热并搅拌至溶解,得到硫酸铝溶液(a1),Al2O3浓度约6g/100ml。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)。将5升蒸馏水加入到2.4升工业级的模数3.0浓水玻璃中,得到稀水玻璃溶液(c)。取一10升的钢制反应罐,罐中加入2升蒸馏水并搅拌加热至70℃后,同时打开分别存有硫酸铝和氨水的容器的阀门,按制备600g无定形硅铝产品设定(a1)的流量以使中和反应时间在40分钟,并迅速调整(b)的流量使体系的pH值保持在9.0,并控制体系的温度在55℃。硫酸铝反应完成后,停止加入氨水,生成的氧化铝溶胶稳定30分钟后,开始加入计量的(c)1.4升,10分钟内加完后,开始体系的老化过程,保持pH值在9.0左右,温度60℃。老化30分钟后,过滤胶体溶液得到湿滤饼,将滤饼重新加蒸馏水打浆水洗,再过滤得到滤饼(d)。将(d)在110℃下干燥8小时后,粉碎、过筛得本发明催化剂所涉及无定形硅铝产品S-1。
实例6
将3.5升一种工业级硫酸铝浓溶液加入到4.0升蒸馏水中,同时加热并搅拌至溶解,得到硫酸铝溶液(a2),Al2O3浓度8g/100ml。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)。取一10升的钢制反应罐,罐中加入2升蒸馏水并搅拌加热至70℃后,同时打开分别存有硫酸铝和氨水的容器的阀门,按制备600g无定形硅铝产品设定(a2)的流量以使中和反应时间在1.5小时,并迅速调整(b)的流量使体系的pH值保持在8.5,并控制体系的温度在55℃。硫酸铝反应完成后,停止加入氨水,生成的氧化铝溶胶稳定15分钟后,按最终含SiO2量开始加入计量的实例5中的(c)6.2升,5分钟内加完后,开始体系的老化过程,保持pH值在8.5,温度65℃。老化15分钟后,过滤胶体溶液得到湿滤饼,将滤饼重新加蒸馏水打浆水洗,再过滤得到滤饼(d)。将(d)再次打浆后,加入31.5ml磷酸,继续搅拌30分钟后过滤得滤饼(e),将(e)在110℃下干燥8小时后,粉碎、过筛得本发明催化剂所涉及的无定形硅铝产品S-2。
实例7
将工业级浓铝酸钠溶液加入到6升蒸馏水中,同时加热并搅拌至溶解,得到铝酸钠溶液(a3),Al2O3浓度18g/100ml。取工业Al2SO4溶液,加入适量蒸馏水稀释成4g/100ml(b)。取一10升的钢制反应罐,罐中加入2升蒸馏水并搅拌加热至70℃后,同时打开分别存有硫酸铝和铝酸钠的容器的阀门,按制备600g无定形硅铝产品设定(a3)的流量以使中和反应时间在一小时,并迅速调整(b)的流量使体系的pH值保持在8.0,并控制体系的温度在60℃。反应完成后,生成的氧化铝溶胶稳定40分钟后,按最终含SiO2量开始加入计量实例5中的(c)3.3升,10分钟内加完后,开始体系的老化过程,保持pH值在8.5,温度50℃。老化40分钟后,过滤胶体溶液得到湿滤饼,将滤饼重新加蒸馏水打浆水洗,再过滤得到滤饼(d)。将(d)在110℃下干燥8小时后,粉碎、过筛得本发明催化剂所涉及的无定形硅铝产品S-3。
实例8
将3.0升浓氯化铝溶液加入到4升蒸馏水中,同时加热并搅拌至溶解,得到氯化铝溶液(a4),折合成A12O3浓度4g/100ml。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)。取一10升的钢制反应罐,罐中加入2升蒸馏水并搅拌加热至70℃后,同时打开分别存有氯化铝和氨水的容器的阀门,按制备600g无定形硅铝产品设定(a4)的流量以使中和反应时间在40分钟,并迅速调整(b)的流量使体系的pH值保持在9.0,并控制体系的温度在55℃。氯化铝反应完成后,停止加入氨水,生成的氧化铝溶胶稳定30分钟后,按最终含SiO2量开始加入计量实例5中的(c)2.0升,10分钟内加完后,开始体系的老化过程,保持pH值在9.0,温度60℃。老化30分钟后,过滤胶体溶液得到湿滤饼,将滤饼重新加蒸馏水打浆水洗,再过滤得到滤饼(d)。将(d)在110℃下干燥8小时后,粉碎、过筛得本发明催化剂所涉及的无定形硅铝产品S-4。
表2.无定形硅铝性质
编号 | SiO2(w%) | 比表面(m2/g) | 孔容(ml/g) | 孔径(nm) | 红外酸度(mmol/l) |
S-1 | 15 | 390 | 0.91 | 9.4 | 0.36 |
S-2 | 45 | 452 | 1.15 | 10.2 | 0.54 |
S-3 | 30 | 403 | 1.01 | 9.7 | 0.31 |
S-4 | 20 | 483 | 1.22 | 10.6 | 0.36 |
实例9
为本发明催化剂所涉及的载体SA及催化剂CATA。称取本发明所涉及的实例5中的S-1无定形硅铝102.5g及本发明所涉及的实例3中Y沸石C60.6g,混匀后加入250g由孔容0.42ml/g的小孔氧化铝加硝酸胶溶的胶冻状粘合剂碾压成团后,放入挤条机中挤条成型后,在110℃干燥10小时,500℃活化4小时制得载体SA后,再用w-Ni共浸渍液使催化剂最终含氧化镍7w%,氧化钨22w%,在110℃干燥12小时,及500℃活化3小时后,得到催化剂CATA。
实例10
为本发明催化剂所涉及的载体SB及催化剂CATB。称取本发明催化剂所涉及实例6中的S-2无定形硅铝126.5g,及本发明催化剂所涉及实例3中的Y沸石C30.5g,混匀后加入250g由孔容0.42ml/g的小孔氧化铝加硝酸胶溶的胶冻状粘合剂碾压成团后,放入挤条机中挤条成型,在100℃干燥11小时,500℃活化4小时制得载体SB后,再用W-Ni共浸渍液浸渍使催化剂最终含氧化镍7w%,氧化钨22w%,110℃干燥12小时,及500℃活化3小时后,得到催化剂CATB。
比较例1
为参比载体SC及催化剂CATC。称取比表面280m2/g、孔容0.76ml/g、SiO2含量35w%的硅铝104.8g(抚顺石化公司催化剂厂生产的一种商业硅铝产品)及实例10所涉及的的同样的Y沸石组分30.5g,混匀后加入250g由孔容0.42ml/g的小孔氧化铝加硝酸胶溶的胶冻状粘合剂碾压成团后,放入挤条机中挤条成型得经干燥、活化载体SC,再用48ml一种W-Ni共浸液饱和浸渍60gC再经干燥、活化得到参比催化剂CATC。其干燥和活化条件与实例9中相同。
比较例2
为参比载体SD及催化剂CATD。称取一种SiO2/Al2O3为12、红外酸度0.94mmol/g的Y沸石(抚顺石化公司催化剂厂生产)30.5g,及一种实例10所涉及的同样的硅铝104.8g,混匀后加入250g由孔容0.42ml/g的小孔氧化铝加硝酸胶溶的胶冻状粘合剂碾压成团后,放入挤条机中挤条成型得经干燥、活化载体SD,再用48ml一种W-Ni共浸液饱和浸渍60gC再经干燥、活化得到参比催化剂CATD。其干燥和活化条件与实例9中相同。
将上述本发明催化剂及其参比催化剂进行评价。评价用原料油为胜利VGO,反应压力14MPa,氢油体积比1500,空速1.5h-1。主要性质见表4。评价通过对比达到相同单程转化率时反应温度的高低来评定加氢裂化催化剂的活性,并根据给定转化率下产品分布的不同来评定催化剂的选择性,中油选择性的计算是按“中间馏分油收率/<370℃产物收率”得到的。
从表3载体及催化剂物化性质看出,比较例的载体及其催化剂孔容及比表面均较低,无疑会影响金属的分散及其加氢活性,并且由于催化剂所使用沸石的酸性过强也使得催化剂的中油选择性提高不大。从表5的评价结果也显示了本发明催化剂在处理一种高芳烃、高干点重质原料油时,保持不低于65v%的转化率,中油选择性一般不低于80%,而反应温度不一般不高于385℃由此说明本发明催化剂在保持较高活性的基础上,具有很好的中油选择性。
表3.载体及催化剂物化性质
表4.原料油的性质
表5.催化剂评价结果
载体/催化剂编号 | A | CATA | B | CATB | C | CATC | D | DATD |
比表面,m2/g | 395 | 256 | 408 | 213 | 303 | 188 | 338 | 208 |
孔容,ml/g | 0.72 | 0.35 | 0.68 | 0.40 | 0.55 | 0.26 | 0.55 | 0.28 |
4-15nm孔分布,% | - | 82.5 | - | 83.3 | - | 79.1 | 68.8 | |
红外酸度,mmol/g | - | 0.41 | - | 0.38 | - | 0.39 | 0.62 |
密度,d4 20 | 0.9066 |
馏程,℃ | |
IBP | 346 |
10% | 388 |
50% | 433 |
90% | 489 |
EP | 526 |
质谱分析,w% | |
链烷烃 | 18.3 |
环烷烃 | 43.1 |
芳 烃 | 34.8 |
胶 质 | 3.8 |
残碳,w% | 0.01 |
S,w% | 0.59 |
N,μg/g | 1419 |
BMCI值 | 43.2 |
催化剂编号 | CATA | CATB | CATC | CATD |
反应温度,℃ | 375 | 380 | 385 | 380 |
中油选择性,% | 80.1 | 82.2 | 78.3 | 74.1 |
Claims (10)
1.一种用于生产中间馏分油的加氢裂化催化剂,含有加氢活性金属组分、Y沸石和无定形硅铝,其特征在于所含的Y沸石为改性超疏水Y沸石,其SiO2/Al2O3摩尔比5-25,晶胞常数2.420~2.445nm,红外酸度0.2-0.6mmol/g,在25℃、P/Po为0.1条件下,水吸附量小于5w%,比表面积600~850m2/g,所含的无定形硅铝的SiO2含量15-50w%,比表面300-600m2/g,孔容0.8-1.5ml/g,红外酸度0.25-0.60mmol/g。
2.按照权利要求1的催化剂,其特征在于所述催化剂的比表面180-300m2/g,孔容0.25-0.45ml/g,红外酸度0.25-0.55mmol/g,4-15nm孔占总孔容的60-90%。
3.按照权利要求1的催化剂,其特征在于所述的Y沸石含量为5-40w%,无定形硅铝含量为10-50w%,氧化铝含量15-30w%,所述的VIB族金属选自Mo、W,按氧化物计含量为10-40w%,VIII金属选自Co、Ni,按氧化物计含量为1-10w%。
4.按权利要求1或2中的催化剂,其特征在于催化剂的比表面200-250m2/g,孔容0.30-0.40ml/g,红外酸度0.35-0.45mmol/g,4-15nm孔占总孔容的70-90%。
5.按权利要求3的催化剂,其特征在于Y沸石含量为10-30w%,无定形硅铝含量为20-40w%,VIB族金属氧化物含量为15-30w%,VIII族金属氧化物含量为4-8w%。
6.按权利要求1的催化剂,其特征在于所说的无定形硅铝含SiO220-40w%,比表面350-550m2/g,孔容0.9-1.4ml/g,红外酸度0.30-0.55mmol/g。
7.按权利要求1或6中催化剂,其特征在于所述的无定形硅铝比表面积400-500m2/g,孔容1.0-1.3ml/g,红外酸度0.35-0.50mmol/g。
8.按权利要求1中的催化剂,其特征在于所述的Y沸石SiO2/Al2O3摩尔比为6.0-17,晶胞常数2.425-2.435nm,>2.0nm二次微孔占总孔的50%以上,比表面700-800m2/g,红外酸度0.30-0.50mmol/g。
9.一种权利要求1催化剂的制备方法,采用常规的催化剂成型和活性金属负载方法,其特征在于所涉及Y沸石的制备方法如下:
(1)制备Na2O含量小于0.2w%的Y沸石I;
(2)将Y沸石产物I置于高温焙烧炉中,在自身水蒸气或通入水蒸气,450℃-700℃,0.01-1.0MPa压力水蒸气下焙烧0.5-10小时,制得SiO2/Al2O3摩尔比为5.2-6.0的超疏水Y沸石;
所涉及的无定形硅铝制备步骤如下:
(a)将一种酸性铝盐溶液与一种碱性沉淀剂并流加入到有少量去离子水的反应容器中,在pH值6.0-10.0,温度50-70℃形成溶胶,中和反应时间为0.5-2小时;
(b)将(a)在pH8-9的条件下稳定0-60分钟;
(c)将一种硅化合物加入到(b)中;
(d)在pH值7.5-9.5,50-70℃下老化(c)10-60分钟;
(e)过滤并洗涤(d);
(f)将(e)于90-120℃下干燥粉碎而获得产品。
10.按权利要求9的方法,其特征在于所述的超疏水Y沸石进一步用化学方法选择性地脱铝,得到SiO2/Al2O3摩尔比为6.5-25的超疏水Y沸石。
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Also Published As
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US6723297B2 (en) | 2004-04-20 |
US20020160906A1 (en) | 2002-10-31 |
US6399530B1 (en) | 2002-06-04 |
KR100478078B1 (ko) | 2005-03-23 |
KR20000035467A (ko) | 2000-06-26 |
CN1096296C (zh) | 2002-12-18 |
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