CN107344107A - A kind of catalyst for hydro-upgrading and preparation method thereof - Google Patents
A kind of catalyst for hydro-upgrading and preparation method thereof Download PDFInfo
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- CN107344107A CN107344107A CN201610289587.1A CN201610289587A CN107344107A CN 107344107 A CN107344107 A CN 107344107A CN 201610289587 A CN201610289587 A CN 201610289587A CN 107344107 A CN107344107 A CN 107344107A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 57
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 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 107
- 239000002808 molecular sieve Substances 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 30
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 15
- 238000009415 formwork Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 27
- 239000002283 diesel fuel Substances 0.000 description 19
- 238000001354 calcination Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000005336 cracking Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 101100228853 Saccharolobus solfataricus (strain ATCC 35092 / DSM 1617 / JCM 11322 / P2) gds gene Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- 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)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of catalyst for hydro-upgrading and preparation method thereof.The catalyst for hydro-upgrading includes hydrogenation active metal component and carrier, and carrier includes Modified Zeolite Y and aluminum oxide, and the property of the Modified Zeolite Y is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.The catalyst for hydro-upgrading is suitable for during hydro-upgrading of inferior diesel, has the characteristics that diesel yield is high and diesel product quality is good.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly one kind can be using poor ignition quality fuel as raw material, and the diesel oil of production has diesel oil hydrogenation modification catalyst that diesel product yield is high, Cetane number is high and density reduction amplitude is big and preparation method thereof.
Background technology
From oil Refining Technologies angle, diesel oil is from normal pressure straight-run diesel oil and the diesel oil distillate of secondary operation production.And the main path of secondary operation technique has catalytic cracking, is hydrocracked and delayed coking.Because diesel quality standard improves year by year, cause catalytic diesel oil inferior（Especially heavy MIP diesel oil, its density are up to 0.95g/cm3More than）It can not meet index request with coker gas oil.How alap investment and operating cost, production environment friendly fuel oil for vehicles, it has also become oil refining enterprise urgently to be resolved hurrily problem are used.
For cleaning diesel production, prior art mainly includes the technologies such as hydrofinishing and MHUG.Hydrofinishing can effectively reduce the sulfur content of modification diesel oil, but to improving Cetane number and reducing T95Temperature capability is limited.MHUG is to utilize suitably to crack diesel oil under conditions of middle pressure, generating portion naphtha and wide cut diesel fuel, and the Cracking Component employed in middle pressure diesel modifying catalyst is mainly modified Y type molecular sieve at present, the deficiencies of effective pore size distribution that the Y type molecular sieve prepared by conventional method of modifying there are beneficial to solid tumor and reaction is not concentrated so that dry large-minded, diesel product the yield of existing diesel modifying catalyst is low, the amplitude of Cetane number raising is small, T95The shortcomings of low and density of point is big.
The method of industrial production Y type molecular sieve is essentially all the directing agent method proposed using GRACE companies of the U.S. in USP 3639099 and USP 4166099 at present, the orifice diameter in the Y type molecular sieve original powder duct of synthesis is 0.74nm × 0.74nm, and its micropore pore volume accounts for more than the 95% of total pore volume.Polycyclic heavy constituent molecular diameter in wax oil hydrogenation cracked stock is generally in more than 1nm, cracking reaction for heavy constituent macromolecular, it is adapted to the macropore range that the preferable duct pore diameter range of its reaction and product diffusion is 2nm ~ 10nm, can be exposed by more accessible acid centre, also the desorption and diffusion of the absorption beneficial to raw material macromolecular and reaction and purpose product, raising molecular sieve cracking are selective simultaneously.To improve the low situation for being unfavorable for wax oil macromolecular reaction of the mesoporous pore volume content of Y type molecular sieve, processing generally is modified to Y type molecular sieve original powder, can obtain the Modified Zeolite Y of different pore passage structures and acid structure.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following two aspects：Selective absorption and reaction.Molecular sieve aperture and overcome molecular sieve crystal surface energy barrier when reactant molecule size is less than, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, be at this moment adsorbed molecule serve through the diffusion in the hole of molecular sieve crystal and cage it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modified molecular screen that pore structure is open, mesoporous content is high and acid site exposure is more can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. and show more superior performance, so as to lift the level of hydrocracking catalyst.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, the composition of the catalyst is aluminum oxide 40wt% ~ 80wt%, 0 ~ 20wt% of amorphous silica-alumina, molecular sieve 5wt% ~ 30wt%, described molecular sieve is 0.40 ~ 0.52mL/g of pore volume, 750 ~ 900m of specific surface area2/ g, 2.420 ~ 2.500nm of lattice constant, silica alumina ratio are 7 ~ 15 Y type molecular sieve.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly using silica-alumina, the predecessor of aluminum oxide and/or aluminum oxide and Y type molecular sieve mixing, shaping and it is calcined, introduces the hydrogenation metal of effective dose in shaping species afterwards.Above-mentioned catalyst uses Modified Zeolite Y, and its desulfurization and denitrification activity are higher, but the amplitude that the yield of gained diesel product is low, the Cetane number of diesel oil improves is small, condensation point is high and density is big.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.The catalyst for hydro-upgrading modifies Cracking Component rich in the Modified Zeolite Y that mesoporous, effective pore sife distribution is more concentrated using a kind of as main, when for poor ignition quality fuel hydrogenation process, has the characteristics that diesel yield is high and diesel product quality is good.
Catalyst for hydro-upgrading provided by the invention, comprising hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and aluminum oxide, and the property of wherein Modified Zeolite Y is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, preferably 15 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume, preferably 80% ~ 95%.
The grain size of described Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In described Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of described Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.5 ~ 1.0mmol/g.
In described Modified Zeolite Y, Na2O weight content is below 0.15wt%.
The property of catalyst for hydro-upgrading of the present invention is as follows：Specific surface area is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
Described hydrogenation active metals are the metal of vib and group VIII, and vib metals are preferably Mu He ∕ or tungsten, and the metal of group VIII is preferably Gu He ∕ or nickel.On the basis of the weight of catalyst, vib metals（In terms of oxide）Content be 15.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 5.0% ~ 8.0%, the content of carrier is 62.0% ~ 80.0%.
Described catalyst for hydro-upgrading carrier, on the basis of the weight of carrier, the content of Modified Zeolite Y is 5% ~ 40%, preferably 10% ~ 35%, and the content of aluminum oxide is 60% ~ 95%, preferably 65% ~ 90%.
The preparation method of catalyst for hydro-upgrading of the present invention, include preparation and the load hydrogenation active metal component of carrier, the preparation process of wherein carrier is as follows：Modified Zeolite Y, aluminum oxide are mixed, shaping, then dries and is calcined, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.05 ~ 0.20MPa, and temperature is 400 ~ 600 DEG C, and processing time is 0.5 ~ 5.0 hour；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing under the conditions of existing for organic formwork agent, then filtered and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the Modified Zeolite Y of the present invention is made.
In the preparation process of Modified Zeolite Y used in the present invention, step（1）The property of described NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio is 3 ~ 6, preferably 4.5 ~ 5.5, and grain size is 1.0 ~ 2.5 μm, and preferably 1.2 ~ 1.8 μm, relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, and specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
The inventive method step（1）In,（NH4）2SiF6Addition be NaY type molecular sieve butt weight 5wt% ~ 20wt%.
The inventive method step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.NaY types molecular sieve with（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, and preferably 90 ~ 120 DEG C, the reaction time is 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The inventive method step（1）In, NaY types molecular sieve with（NH4）2SiF6After aqueous solution contact is reacted, molecular sieve and accessory substance are separated, can be washed, refiltered, dry, the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after preferably drying.Dry condition is usually to be dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C.
The inventive method step（2）In, hydro-thermal process is to use saturated steam processing step（1）In obtained molecular sieve, treatment conditions：0.05 ~ 0.20MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, preferably 400 ~ 600 DEG C of temperature, 450 ~ 600 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.
The inventive method step（3）In, organic formwork agent is the one or more in tetraethyl ammonium hydroxide, TMAH, TPAOH.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, carry out hydrothermal crystallizing, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of the organic formwork agent aqueous solution is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, and gauge pressure is 0.1 ~ 0.2MPa.After crystallization, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：1 ~ 10h is dried at 50 ~ 110 DEG C.
In the inventive method, step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere, and wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.Typically using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min for roasting.
Y type molecular sieve in catalyst for hydro-upgrading of the present invention is to use（NH4）2SiF6Processing is modified to NaY molecular sieve, while modulation molecular sieve silica alumina ratio is realized, sodium ion in NaY molecular sieve can be deviate from together, then hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, part silicon atom and aluminium atom can be so set to enter framework of molecular sieve structure under organic formwork agent effect, while further stablizing and improving the skeleton structure of modified molecular screen, eliminate caused non-skeleton structure in zeolite-water heat treatment process, unimpeded pore passage structure, part organic formwork agent can be also entered in the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can be by the controllable removing in order of the organic formwork agent in molecular sieve, so as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve in catalyst for hydro-upgrading of the present invention, acidity is suitable, crystallinity is high, mesoporous proportion is high, pore-size distribution is more concentrated, suitably as Cracking Component.Because the Y type molecular sieve has bigger pore volume and mesopore volume, more acid centres are exposed, be advantageous to raw material heavy oil macromolecular to be cracked, but also with more preferably pore size distribution range, the cracking degree of reactant can be efficiently controlled, and be advantageous to product and be diffused in duct, so in cracking reaction, can relative increase activated centre, and the cracking reaction of heavy oil macromolecular progress suitable degree can be made, both the cracking capability of heavy oil had been improved, while has reduced coke yield, catalyst can show good cracking activity and product selectivity.
When catalyst for hydro-upgrading of the present invention is used for poor ignition quality fuel modification, particularly in middle press strip part（4~12MPa）Lower processing poor ignition quality fuel（Heavy MIP diesel oil and coker gas oil）With very high catalytic activity and diesel yield, the Cetane number for modifying diesel oil can be increased substantially, the density of diesel product is effectively reduced, and can meet refinery's increase operating flexibility, increase device disposal ability, the needs for the diesel oil that further raises productivity and improves the quality.
Brief description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of embodiment 1；
Fig. 2 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of comparative example 1；
Fig. 3 is the XRD diffraction patterns of the gained Modified Zeolite Y of embodiment 1.
Embodiment
Aluminum oxide can use aluminum oxide used in conventional hydro modifying catalyst, such as macroporous aluminium oxide in catalyst for hydro-upgrading of the present invention.The pore volume of macroporous aluminium oxide used is 0.7 ~ 1.0mL/g, and specific surface area is 200 ~ 500m2/g。
Conventional shaping assistant such as peptization acid, extrusion aid etc. can also be added in catalyst carrier preparation process of the present invention.
Detailed process prepared by catalyst for hydro-upgrading carrier of the present invention is：
Modified Zeolite Y, aluminum oxide are mixed, shaping, is then dried and is calcined, be prepared into carrier, described drying can be dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
In catalyst for hydro-upgrading of the present invention, the load of active metal can use carrying method conventional in the prior art, it is preferred that infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e. with the solution impregnated catalyst carrier containing required active component, then carrier after dipping is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, final catalyst is made in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to the scope of these embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, and relative crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses XRF methods（X ray fluorescence spectrometry）Measure, the grain size of molecular sieve use SEM（SEM）Mode determine.Meleic acid amount uses Pyridine adsorption IR spectra method, and sodium content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example is industrially prepared, and property is as follows：SiO2/Al2O3Mol ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2O weight content is 6.5wt%, specific surface area 856m2/ g, total pore volume 0.32mL/g, micropore pore volume account for the 81.3% of total pore volume, butt 72.0wt%.
Embodiment 1
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 78g/L's that 410mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.15MPa, 530 DEG C of temperature, under conditions of 1.5 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentrations are 7.5%, constant temperature stirs 2 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 100 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 8 hours, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-1, molecular sieve property are listed in table 1.
Embodiment 2
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 58g/L's that 256mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 65.0wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.10MPa, 450 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 369mL mass concentrations are 4.8%, constant temperature stirs 2 hours under the conditions of 85 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 65v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 390 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-2, molecular sieve property are listed in table 1.
Embodiment 3
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 78g/L's that 410mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.15MPa, 480 DEG C of temperature, under the conditions of 1.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 520mL mass concentrations are 5.3%, constant temperature stirs 4 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 420 DEG C, and the constant temperature calcining time is 6 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-3, molecular sieve property are listed in table 1.
Embodiment 4
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.0wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.10MPa, 580 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the TPAOH aqueous solution that 910mL mass concentrations are 7.5%, constant temperature stirs 4 hours under the conditions of 90 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 65v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4, molecular sieve property are listed in table 1.
Comparative example 1
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature is stirred 2 hours, and constant temperature is filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Molecular sieve is calcined 3 hours by temperature programming at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；The molecular sieve after second of ammonium exchange of 100g is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentrations are 7.5%, constant temperature stirs 2 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C of crystallization temperature, gauge pressure is 0.1MPa, crystallization time 8 hours, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature is stirred 2 hours, and constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Molecular sieve is calcined 3 hours by temperature programming at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；The molecular sieve after second of ammonium exchange of 100g is taken to be put into the dust technology that 800mL concentration is 0.3mol/L, constant temperature stirs 2 hours under the conditions of 80 DEG C, and constant temperature is filtered after terminating and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.20MPa, 530 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process obtain molecular sieve；Sample number into spectrum LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3 are prepared using the method for embodiment in CN201510147788.3 1, molecular sieve property is listed in table 1.
Table 1
The property of Y type molecular sieve
| Production code member | LAY-1 | LAY-2 | LAY-3 | LAY-4 |
| Specific surface area, m2/g | 896 | 859 | 890 | 902 |
| Pore volume, cm3/g | 0.69 | 0.60 | 0.73 | 0.78 |
| Lattice constant, nm | 2.441 | 2.444 | 2.442 | 2.436 |
| Relative crystallinity, % | 123 | 134 | 129 | 122 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 48.6 | 28.6 | 33.5 | 17.3 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 82 | 89 | 86 | 90 |
| Infrared total acid content, mmol/g | 0.84 | 0.88 | 0.71 | 0.62 |
| Na2O, wt% | 0.05 | 0.06 | 0.06 | 0.08 |
Continued 1
| Production code member | LDAY-1 | LDAY-2 | LDAY-3 |
| Specific surface area, m2/g | 633 | 712 | 603 |
| Pore volume, cm3/g | 0.44 | 0.38 | 0.38 |
| Lattice constant, nm | 2.439 | 2.436 | 2.449 |
| Relative crystallinity, % | 98 | 103 | 86 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 7.5 | 33.5 | 8.6 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 47 | 34 | 37 |
| Infrared total acid content, mmol/g | 0.77 | 0.41 | 0.71 |
| Na2O, wt% | 0.21 | 0.19 | 0.45 |
Embodiment 5
By 44.4 grams of LAY-1 molecular sieves（Butt 90wt%）, 228.6 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 171.4 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier GDS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FC-1, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 88.9 grams of LAY-2 molecular sieves（Butt 90wt%）, 171.4 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 184.1 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier GDS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FC-2, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7
By 33.3 grams of LAY-3 molecular sieves（Butt 90wt%）, 242.9 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 168.8 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier GDS-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FC-3, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 8
By 111.1 grams of LAY-4 molecular sieves（Butt 90wt%）, 142.9 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 190.4 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier GDS-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FC-4, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 4 ~ 6
According to the method for embodiment 6, LAY-2 being changed into LDAY-1, LDAY-2, LDAY-3 respectively, carrier DGDS-1, DGDS-2, DGDS-3 and catalyst DFC-1, DFC-2, DFC-3 being made, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 9 ~ 12
This embodiment describes catalyst FC-1, FC-2, FC-3 and FC-4 of the present invention Activity evaluation.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700：1, volume space velocity 2.0h during liquid-1, using catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 3, and evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes comparative example catalyst DFC-1, DFC-2, DFC-3 of the present invention Activity evaluation.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700：1, volume space velocity 2.0h during liquid-1, using catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 3, and evaluation result is listed in table 4.
Table
2
The composition and physico-chemical property of catalyst carrier and catalyst
| Carrier forms and property | ||||
| Numbering | GDS-1 | GDS-2 | GDS-3 | GDS-4 |
| Composition | ||||
| Modified Zeolite Y, wt% | 20 | 40 | 15 | 35 |
| Aluminum oxide, wt% | Surplus | Surplus | Surplus | Surplus |
| Property | ||||
| Specific surface area, m2/g | 535 | 587 | 497 | 601 |
| Pore volume, mL/g | 0.81 | 0.71 | 0.77 | 0.67 |
| Catalyst forms and property | ||||
| Numbering | FC-1 | FC-2 | FC-3 | FC-4 |
| WO3, wt% | 23.3 | 24.1 | 19.9 | 21.6 |
| NiO, wt% | 5.7 | 5.8 | 4.8 | 5.4 |
| Specific surface area, m2/g | 363 | 399 | 355 | 389 |
| Pore volume, mL/g | 0.54 | 0.51 | 0.52 | 0.49 |
Continued
2
| Carrier forms and property | |||
| Numbering | DGDS-1 | DGDS-2 | DGDS-3 |
| Composition | |||
| Modified Zeolite Y, wt% | 40 | 40 | 40 |
| Aluminum oxide, wt% | Surplus | Surplus | Surplus |
| Property | |||
| Specific surface area, m2/g | 391 | 344 | 358 |
| Pore volume, mL/g | 0.55 | 0.54 | 0.47 |
| Catalyst forms and property | |||
| Numbering | DFC-1 | DFC-2 | DFC-3 |
| WO3, wt% | 24.2 | 24.0 | 24.1 |
| NiO, wt% | 6.0 | 5.9 | 5.8 |
| Specific surface area, m2/g | 0.36 | 0.40 | 0.38 |
| Pore volume, mL/g | 272 | 251 | 260 |
Table
3
Raw material oil nature
| Feedstock oil | MIP catalytic diesel oils |
| Density (20 DEG C), g/cm3 | 0.9537 |
| Boiling range, DEG C | |
| IBP/10% | 200/234 |
| 30%/50% | 256/277 |
| 70%/90% | 305/348 |
| 95%/EBP | 363/367 |
| Condensation point, DEG C | 5 |
| Sulphur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | <20.0 |
| C, wt% | 88.49 |
| H, wt% | 11.04 |
Table
4
Catalyst performance comparative evaluation's result
| Catalyst | FC-1 | FC-2 | FC-3 | FC-4 |
| Feedstock oil | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils |
| Operating condition | ||||
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 | 2.0 |
| React stagnation pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 700:1 | 700:1 | 700:1 | 700:1 |
| Reaction temperature, DEG C | 372 | 363 | 370 | 367 |
| Product yield and property | ||||
| Naphtha | ||||
| Yield, wt% | 2.4 | 2.3 | 2.2 | 1.9 |
| Virtue is latent, wt% | 57.2 | 58.6 | 58.9 | 60.2 |
| Diesel oil | ||||
| Yield, wt% | 96.0 | 96.5 | 96.2 | 97.2 |
| Density (20 DEG C), g/cm3 | 0.8355 | 0.8368 | 0.8377 | 0.8391 |
| T95, DEG C | 343 | 345 | 345 | 347 |
| Cetane number | 38.3 | 39.2 | 40.1 | 40.8 |
| Sulphur, μ g/g | 5 | 8 | 4 | 4 |
| Liquid is received, wt% | 98.4 | 98.8 | 98.4 | 99.1 |
Continued
4
| Catalyst | DFC-1 | DFC-2 | DFC-3 |
| Feedstock oil | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils |
| Operating condition | |||
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 |
| React stagnation pressure, MPa | 10.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 700:1 | 700:1 | 700:1 |
| Reaction temperature, DEG C | 373 | 386 | 389 |
| Product yield and property | |||
| Naphtha | |||
| Yield, wt% | 3.9 | 4.3 | 4.6 |
| Virtue is latent, wt% | 51.2 | 50.0 | 47.9 |
| Diesel oil | |||
| Yield, wt% | 92.9 | 91.7 | 88.2 |
| Density (20 DEG C), g/cm3 | 0.8595 | 0.8509 | 0.8501 |
| T95, DEG C | 353 | 354 | 352 |
| Cetane number | 31.0 | 30.4 | 31.3 |
| Sulphur, μ g/g | 22 | 19 | 15 |
| Liquid is received, wt% | 96.8 | 96.0 | 93.1 |
When it can be seen from the evaluation result of table 4 using catalyst for hydro-upgrading of the present invention, diesel yield and product quality are superior to reference catalyst.
Claims (22)
1. a kind of catalyst for hydro-upgrading, comprising hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and aluminum oxide, and the property of wherein Modified Zeolite Y is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.
2. according to the catalyst described in claim 1, it is characterised in that：The property of the Y type molecular sieve is as follows：SiO2/Al2O3Mol ratio is 15 ~ 50, and total pore volume is 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.
3. according to the catalyst described in claim 1, it is characterised in that：The grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
4. according to the catalyst described in claim 1, it is characterised in that：The mesoporous bore dia of the Y type molecular sieve is 2nm ~ 10nm.
5. according to the catalyst described in claim 1, it is characterised in that：The specific surface area of the Y type molecular sieve is 650m2/g~1000m2/ g, preferably 750m2/g~1000m2/g。
6. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid content of the Y type molecular sieve is 0.5 ~ 1.0 mmol/g.
7. according to the catalyst described in claim 1, it is characterised in that：In the Y type molecular sieve, Na2O weight content is below 0.15wt%.
8. according to the catalyst described in claim 1, it is characterised in that：The property of the catalyst for hydro-upgrading is as follows：Specific surface area is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
9. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are the metal of vib and group VIII, and vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；On the basis of the weight of catalyst, vib metals are using the content that oxide is counted as 15.0% ~ 30.0%, and for group VIII metal using the content that oxide is counted as 5.0% ~ 8.0%, the content of carrier is 62.0% ~ 80.0%.
10. according to the catalyst described in claim 1 or 9, it is characterised in that：Described catalyst for hydro-upgrading carrier, on the basis of the weight of carrier, the content of Modified Zeolite Y is 5% ~ 40%, and the content of aluminum oxide is 60% ~ 95%, is preferably as follows：The content of Modified Zeolite Y is 10% ~ 35%, and the content of aluminum oxide is 65% ~ 90%.
11. the preparation method of any catalyst of claim 1 ~ 10, including the preparation of carrier and load hydrogenation active metal component, the preparation process of wherein carrier it is as follows：Modified Zeolite Y, aluminum oxide are mixed, shaping, then dries and is calcined, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.05 ~ 0.20MPa, and temperature is 400 ~ 600 DEG C, and processing time is 0.5 ~ 5.0 hour, and preferably hydrothermal conditions are as follows：Gauge pressure is 0.05 ~ 0.20MPa, and temperature is 450 ~ 600 DEG C, and processing time is 1.0 ~ 3.0 hours；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing under the conditions of existing for organic formwork agent, then filtered and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and Modified Zeolite Y is made.
12. according to claim 11 methods described, it is characterised in that：Step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio is 3 ~ 6, and grain size is 1.0 ~ 2.5 μm, and preferably 1.2 ~ 1.8 μm, relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, and specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
13. according to claim 11 methods described, it is characterised in that：Step（1）In,（NH4）2SiF6Addition be NaY type molecular sieve butt weight 5wt% ~ 20wt%.
14. according to claim 11 methods described, it is characterised in that：Step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.
15. according to claim 11 methods described, it is characterised in that：Step（1）In, NaY types molecular sieve with（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour, and preferred reaction conditions are as follows：Temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
16. according to claim 11 methods described, it is characterised in that：Step（1）In, dry condition is dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C, and the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after drying.
17. according to claim 11 methods described, it is characterised in that：Step（3）In, organic formwork agent is the one or more in tetraethyl ammonium hydroxide, TMAH, TPAOH.
18. according to claim 11 methods described, it is characterised in that：By step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, carry out hydrothermal crystallizing, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of the organic formwork agent aqueous solution is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, and gauge pressure is 0.1 ~ 0.2MPa.
19. according to claim 11 methods described, it is characterised in that：Step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere, and wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.
20. according to claim 11 methods described, it is characterised in that：Described aluminum oxide uses macroporous aluminium oxide, and its property is as follows：0.7 ~ 1.0mL/g of pore volume, 200 ~ 500m of specific surface area2/g。
21. according to claim 11 methods described, it is characterised in that：Process prepared by the catalyst for hydro-upgrading carrier is：
Modified Zeolite Y, aluminum oxide are mixed, shaping, is then dried and is calcined, is prepared into carrier, described drying is dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
22. according to claim 11 methods described, it is characterised in that：In the catalyst for hydro-upgrading, the load of active metal uses infusion process, i.e., with the solution impregnated catalyst carrier containing active metal component, in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour after dipping, then it is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, catalyst for hydro-upgrading is made.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938088A (en) * | 2004-03-03 | 2007-03-28 | 国际壳牌研究有限公司 | Catalyst carrier and catalyst composition, processes for their preparation and their use |
| CN101723399A (en) * | 2008-10-10 | 2010-06-09 | 中国石油天然气集团公司 | Preparation method of skeleton silicon-rich Y-shaped molecular sieve |
| CN102049283A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
| CN103003202A (en) * | 2010-05-14 | 2013-03-27 | 墨西哥石油研究院 | Process for altering the physico-chemical properties of faujasite Y-type zeolites |
| CN103100416A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Diesel oil hydro-upgrading catalyst and preparation method thereof |
| CN103172082A (en) * | 2013-04-25 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of mesoporous-containing Y-shaped molecular sieve |
| CN104043473A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst and use thereof |
| CN104591214A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Small grain Y type molecular sieve and its preparation method |
| CN104667955A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A catalyst for hydrogenation modification and a preparing method thereof |
| CN104667967A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Diesel hydroupgrading catalyst and preparation method thereof |
-
2016
- 2016-05-05 CN CN201610289587.1A patent/CN107344107B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938088A (en) * | 2004-03-03 | 2007-03-28 | 国际壳牌研究有限公司 | Catalyst carrier and catalyst composition, processes for their preparation and their use |
| CN101723399A (en) * | 2008-10-10 | 2010-06-09 | 中国石油天然气集团公司 | Preparation method of skeleton silicon-rich Y-shaped molecular sieve |
| CN102049283A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
| CN103003202A (en) * | 2010-05-14 | 2013-03-27 | 墨西哥石油研究院 | Process for altering the physico-chemical properties of faujasite Y-type zeolites |
| CN103100416A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Diesel oil hydro-upgrading catalyst and preparation method thereof |
| CN104043473A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst and use thereof |
| CN103172082A (en) * | 2013-04-25 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of mesoporous-containing Y-shaped molecular sieve |
| CN104591214A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Small grain Y type molecular sieve and its preparation method |
| CN104667955A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A catalyst for hydrogenation modification and a preparing method thereof |
| CN104667967A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Diesel hydroupgrading catalyst and preparation method thereof |
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