CN107344107B - 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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- CN107344107B CN107344107B CN201610289587.1A CN201610289587A CN107344107B CN 107344107 B CN107344107 B CN 107344107B CN 201610289587 A CN201610289587 A CN 201610289587A CN 107344107 B CN107344107 B CN 107344107B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 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 29
- 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 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 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 106
- 239000002808 molecular sieve Substances 0.000 claims description 105
- 238000000034 method Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000009415 formwork Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001802 infusion 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
- 230000035484 reaction time Effects 0.000 claims 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- -1 carrier Component Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 description 27
- 239000003921 oil Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 238000001354 calcination Methods 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005336 cracking Methods 0.000 description 10
- 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
- 238000011156 evaluation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910004074 SiF6 Inorganic materials 0.000 description 6
- 238000001228 spectrum 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
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 210000004027 cell Anatomy 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
- 238000007654 immersion Methods 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011734 sodium Substances 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
- 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-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
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052738 indium Inorganic materials 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
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000000908 ammonium hydroxide Substances 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
- 239000006227 byproduct Substances 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
- 239000000470 constituent Substances 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
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012263 liquid product Substances 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
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000006250 specific catalysis Methods 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
Images
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
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (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 aluminium oxide, and the property of the Modified Zeolite Y is as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3Molar 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 70% of total pore volume or more.The catalyst for hydro-upgrading is suitable for during hydro-upgrading of inferior diesel, has the characteristics that diesel yield height and diesel product are high-quality.
Description
Technical field
It can be original with poor ignition quality fuel the present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, especially one kind
Material, the diesel oil of production have the diesel oil hydrogenation modification catalysis that diesel product yield is high, Cetane number is high and density reduction amplitude is big
Agent and preparation method thereof.
Background technique
From oil Refining Technologies angle, diesel oil distillate of the diesel oil from normal pressure straight-run diesel oil and secondary operation production.And it is secondary
The main path of processing technology has catalytic cracking, is hydrocracked and delayed coking.Since diesel quality standard improves year by year, cause
(especially heavy MIP diesel oil, density are up to 0.95g/cm to catalytic diesel oil inferior3More than) and coker gas oil have been unable to meet finger
Mark requires.How alap investment and operating cost, the fuel oil for vehicles of production environment close friend, it has also become oil refining enterprise used
Project urgently to be resolved.
For cleaning diesel production, the prior art mainly includes the technologies such as hydrofinishing and Medium Pressure Hydrogenation Modification.Add hydrogen smart
The sulfur content of modification diesel oil can be effectively reduced in system, but to improvement Cetane number and reduces T95Temperature capability is limited.Medium pressure hydrogenation changes
Matter is to utilize suitably to crack diesel oil under conditions of middle pressure, generating portion naphtha and wide cut diesel fuel, and middle pressure bavin at present
Cracking Component employed in oily modifying catalyst is mainly modified Y type molecular sieve, the Y type point prepared by conventional method of modifying
The deficiencies of son sieve is not concentrated there are the effective pore size distribution for being conducive to solid tumor and reaction, so that existing diesel modifying catalyst
Do that the amplitude that large-minded, diesel product yield is low, Cetane number improves is small, T95The disadvantages of low and density of point is big.
The method of industrial production Y type molecular sieve is essentially all using GRACE company, the U.S. in 3639099 He of USP at present
The directing agent method proposed in USP 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis be 0.74nm ×
0.74nm, micropore pore volume account for about 95% of total pore volume or more.Polycyclic recombination fractionated molecule in wax oil hydrogenation cracked stock is straight
Diameter is usually in 1nm or more, cracking reaction for heavy constituent macromolecular, it is suitble to react and the ideal duct aperture of product diffusion
Range is the macropore range of 2nm ~ 10nm, can be exposed by more accessible acid centre, while being also conducive to raw material and dividing greatly
The absorption of son and the desorption and diffusion of reaction and purpose product improve molecular sieve cracking selectivity.It is situated between to improve Y type molecular sieve
Hole pore volume content low the case where being unfavorable for wax oil macromolecular reaction, processing usually is modified to Y type molecular sieve original powder, can be obtained
To the Modified Zeolite Y of different cellular structures and acid structure.
From the point of view of application of the molecular sieve with cracking function during Industrial Catalysis, performance depends primarily on following
Two aspects: selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface
Energy barrier can just diffuse into molecular sieve pore passage, and specific catalysis reaction occurs, is at this moment adsorbed molecule across molecular sieve crystal
Hole and cage diffusion serve it is conclusive.The molecular sieve total pore volume and mesoporous pore volume of conventional method of modifying preparation
It is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modification point that pore structure is open, mesoporous content is high and acid site exposure is more
Son sieve is capable of handling the raw material that molecule is bigger, oil product is heavier, and raising macromolecular conversion probability etc. shows more superior
Performance, to promote the level of hydrocracking catalyst.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, the group of the catalyst become aluminium oxide 40wt% ~
80wt%, 0 ~ 20wt% of amorphous silica-alumina, molecular sieve 5wt% ~ 30wt%, the molecular sieve are 0.40 ~ 0.52mL/g of pore volume, than
750 ~ 900m of surface area2/ g, 2.420 ~ 2.500nm of lattice constant, the Y type molecular sieve that silica alumina ratio is 7 ~ 15.CN101463271A
A kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof is disclosed, silica-alumina, aluminium oxide are mainly used
And/or predecessor and the Y type molecular sieve mixing, molding and roasting of aluminium oxide, a effective amount of plus hydrogen gold is introduced in molding species later
Belong to.Above-mentioned catalyst is all made of Modified Zeolite Y, and desulfurization and denitrification activity are higher, but the yield of gained diesel product it is low,
The amplitude that the Cetane number of diesel oil improves is small, condensation point is high and density is big.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of catalyst for hydro-upgrading and its preparation sides
Method.The catalyst for hydro-upgrading is using a kind of Modified Zeolite Y more concentrated rich in mesoporous, effective pore sife distribution as main
Cracking Component is modified, when being used for poor ignition quality fuel hydrogenation process, has the characteristics that diesel yield height and diesel product are high-quality.
Catalyst for hydro-upgrading provided by the invention, includes hydrogenation active metal component and carrier, and carrier includes modified Y type
Molecular sieve and aluminium oxide, wherein the property of Modified Zeolite Y is as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3It rubs
, than being 10 ~ 50, preferably 15 ~ 50, cell parameter is 2.436 ~ 2.445nm for you, and total pore volume is 0.55 ~ 1.0mL/g, preferably
0.6 ~ 1.0mL/g, mesoporous pore volume account for 70% of total pore volume or more, preferably 80% ~ 95%.
The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In the Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of the Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of the Modified Zeolite Y is 0.5 ~ 1.0mmol/g.
In the Modified Zeolite Y, Na2The weight content of O is 0.15wt% or less.
The property of catalyst for hydro-upgrading of the present invention is as follows: specific surface area is 330 ~ 500m2/ g, pore volume be 0.35 ~
0.55mL/g。
The hydrogenation active metals are the metal of group VIB and group VIII, vib metals be preferably Mu He ∕ or
Tungsten, the metal of group VIII are 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%, the content of group VIII metal (in terms of oxide) is 5.0% ~ 8.0%, and the content of carrier is
62.0%~80.0%。
The 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%, the content of aluminium oxide is 60% ~ 95%, preferably 65% ~ 90%.
The preparation method of catalyst for hydro-upgrading of the present invention, preparation and load hydrogenation active metal component including carrier,
Wherein the preparation process of carrier is as follows: Modified Zeolite Y, aluminium oxide being mixed, molding, then dry and roasting is made and urges
Agent carrier, wherein the preparation method of Modified Zeolite Y, includes the following steps:
(1) NaY type molecular sieve and (NH4)2SiF6Aqueous solution contact is reacted, and is filtered and is dried after reaction；
(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure be 0.05 ~
0.20MPa, temperature are 400 ~ 600 DEG C, and the processing time is 0.5 ~ 5.0 hour；
(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, so
By filtering and drying；
(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, modification Y type point of the invention is made
Son sieve.
In the preparation process of Modified Zeolite Y used in the present invention, the property of NaY type molecular sieve described in step (1) is such as
Under:
SiO2/Al2O3Molar ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm,
Relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, than
Surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for 75% of total pore volume or more.
In the method for the present invention step (1), (NH4)2SiF6Additional amount be NaY type molecular sieve dry weight 5wt% ~
20wt%。
In the method for the present invention step (1), (NH4)2SiF6The mass concentration of aqueous solution is 50 ~ 100g/L.NaY type molecular sieve
With (NH4)2SiF6Aqueous solution contacts the reaction condition that is reacted: temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, when reaction
Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (1), NaY type molecular sieve and (NH4)2SiF6After aqueous solution contact is reacted, separation point
Son sieve and by-product, can wash, refilter, dry, it is preferably dry after resulting Y type molecular sieve butt be 60wt% ~
80wt%.Dry condition is usually 0.5 ~ 5.0 hour dry at 50 ~ 95 DEG C.
In the method for the present invention step (2), hydro-thermal process is the molecular sieve obtained in saturated steam processing step (1),
Treatment conditions: 0.05 ~ 0.20MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, 400 ~ 600 DEG C of temperature, preferably 450 ~ 600 DEG C, place
The reason time 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (3), organic formwork agent is tetraethyl ammonium hydroxide, tetramethylammonium hydroxide, tetrapropyl
One or more of ammonium hydroxide.Wherein, after evenly mixing by Y type molecular sieve obtained in step (2) and organic formwork agent,
Hydrothermal crystallizing is carried out, process is as follows: Y type molecular sieve obtained in step (2) being beaten in organic formwork agent aqueous solution, liquid is solid
Weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of organic formwork agent aqueous solution is
3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, gauge pressure
For 0.1 ~ 0.2MPa.After crystallization, being filtered and being dried can be carried out using conventional method, and generally dry condition is as follows: 50 ~
Dry 1 ~ 10h at 110 DEG C.
In the method for the present invention, step (4) is roast under low temperature oxygen-enriched atmosphere by the Y type molecular sieve that step (3) obtains,
Wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 5 ~ 10h.Roasting is general
Using the method roasted under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.
Y type molecular sieve in catalyst for hydro-upgrading of the present invention is using (NH4)2SiF6Place is modified to NaY molecular sieve
Reason, while realizing modulation molecular sieve silica alumina ratio, can deviate from together the sodium ion in NaY molecular sieve, then in organic mould
Hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of plate agent, part silicon atom and aluminium atom can be made in organic mould in this way
Plate agent effect is lower to enter framework of molecular sieve structure, while further stablizing and improving the skeleton structure of modified molecular screen, disappears
Except the non-skeleton structure generated in zeolite-water heat treatment process, unimpeded cellular structure, part organic formwork agent is also able to enter
Into the duct of molecular sieve, cooperates subsequent oxygen-enriched low-temperature treatment, the organic formwork agent in molecular sieve controllably can orderly be removed,
To generate 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 for, crystallinity is high, mesoporous proportion is high, hole
Diameter distribution is more concentrated, and is suitable for as Cracking Component.Since the Y type molecular sieve has bigger pore volume and mesopore volume, more
More acid centres are exposed, and are conducive to raw material heavy oil macromolecular and are cracked, but also have more preferably pore-size distribution model
It encloses, the cracking degree of reactant can be efficiently controlled, and be conducive to product and be diffused in duct, in this way in cracking reaction
In, can relative increase activated centre, and can make heavy oil macromolecular carry out suitable degree cracking reaction, both improved splitting for heavy oil
Change ability, while coke yield is reduced, catalyst can show good cracking activity and product selectivity.
When catalyst for hydro-upgrading of the present invention is modified for poor ignition quality fuel, especially under middle press strip part (4 ~ 12MPa)
Managing poor ignition quality fuel (heavy MIP diesel oil and coker gas oil) has very high catalytic activity and diesel yield, can increase substantially
The Cetane number of diesel oil is modified, the density of diesel product is effectively reduced, and is able to satisfy refinery and is increased operating flexibility, increases dress
Set the needs of processing capacity, the diesel oil that further raises productivity and improves the quality.
Detailed description of the invention
Fig. 1 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of embodiment；
Fig. 2 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of comparative example；
Fig. 3 is the XRD diffraction pattern of 1 gained Modified Zeolite Y of embodiment.
Specific embodiment
Aluminium oxide can use aluminium oxide used in conventional hydro modifying catalyst in catalyst for hydro-upgrading of the present invention,
Such as macroporous aluminium oxide.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 can also be added in catalyst carrier preparation process of the present invention
Deng.
The detailed process of catalyst for hydro-upgrading carrier preparation of the present invention are as follows:
Modified Zeolite Y, aluminium oxide are mixed, then molding is dried and roasts, is prepared into carrier, described
Drying can be dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
In catalyst for hydro-upgrading of the present invention, carrying method conventional in the prior art is can be used in the load of active metal,
It is preferred that infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., is carried with the solution impregnation catalyst containing required active component
Body, carrier after dipping 100 DEG C ~ 150 DEG C drying 1 ~ 12 hour, then roasted 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, system
Obtain final catalyst.
The following examples are for being described in more detail technical solution of the present invention, but the scope of the present invention is not limited solely to this
The range of a little 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, relatively
Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio is measured using XRF method (x ray fluorescence spectrometry), molecular sieve
Grain size using SEM(scanning electron microscope) by the way of measure.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium
Content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example be it is industrially prepared, property is as follows: SiO2/
Al2O3Molar ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2The weight of O contains
Amount 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, do
Base 72.0wt%.
Embodiment 1
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 95 DEG C, start that (NH is added dropwise into molecular sieve pulp4)2SiF6Aqueous solution dropped evenly the (NH that 410mL solution concentration is 78g/L at 60 minutes4)2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, is filtered and is dried after constant temperature, and the butt of molecular sieve is 63.8wt% after drying；After above-mentioned drying
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.15MPa, 530 DEG C of temperature, processing the time 1.5 hours under conditions of to point
Son sieve carries out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into the tetraethyl hydrogen that 650mL mass concentration is 7.5%
It aoxidizes in aqueous ammonium, constant temperature stirs 2 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal
Crystallization, 100 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 8 hours, is filtered and is dried after crystallization；It will be brilliant
To change obtained drying sample to roast under oxygen-enriched state, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min,
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 is listed in table 1.
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp
(NH4)2SiF6Aqueous solution dropped evenly the (NH that 256mL solution concentration is 58g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition
Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 65.0wt% after drying；It will be above-mentioned dry
Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.10MPa, 450 DEG C of temperature, processing 2.0 hours time condition
Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 369mL mass concentration is 4.8%
In ethyl ammonium hydroxide aqueous solution, under the conditions of 85 DEG C constant temperature stir 2 hours, then by mixed material be transferred in crystallizing kettle into
Row hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and dries place after crystallization
Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 65v%, heating rate in calcination atmosphere
For 1 DEG C/min, 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
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 95 DEG C, start that (NH is added dropwise into molecular sieve pulp4)2SiF6Aqueous solution dropped evenly the (NH that 410mL solution concentration is 78g/L at 60 minutes4)2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, is filtered and is dried after constant temperature, and the butt of molecular sieve is 63.8wt% after drying；After above-mentioned drying
Molecular sieve is added in hydrothermal treatment device, to molecule under the conditions of gauge pressure 0.15MPa, 480 DEG C of temperature, processing the time 1.0 hours
Sieve carries out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into the tetraethyl hydrogen-oxygen that 520mL mass concentration is 5.3%
Change in aqueous ammonium, constant temperature stirs 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance
Change, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and is dried after crystallization；By hydro-thermal
The drying sample that crystallization obtains roasts under oxygen-enriched state, in calcination atmosphere oxygen content be 70v%, heating rate be 1 DEG C/
Min, constant temperature calcining temperature are 420 DEG C, and the constant temperature calcining time is 6 hours, obtain molecular sieve of the present invention.Sample number into spectrum LAY-3, point
Son sieve property is listed in table 1.
Embodiment 4
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp
(NH4)2SiF6Aqueous solution dropped evenly the (NH that 182mL solution concentration is 55g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition
Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.0wt% after drying；It will be above-mentioned dry
Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.10MPa, 580 DEG C of temperature, processing 2.0 hours time condition
Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 910mL mass concentration is 7.5%
In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 4 hours, then by mixed material be transferred in crystallizing kettle into
Row hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and dries place after crystallization
Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 65v%, heating rate in calcination atmosphere
For 1 DEG C/min, 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
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature
Stirring 2 hours, is filtered after constant temperature, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming
Molecular sieve is roasted 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Second of ammonium of 100g is taken to hand over
Molecular sieve after changing is put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentration is 7.5%, permanent under the conditions of 80 DEG C
Mixed material, is then transferred in crystallizing kettle and carries out crystallization by temperature stirring 2 hours, and 100 DEG C of crystallization temperature, gauge pressure 0.1MPa,
It crystallization time 8 hours, is filtered and is dried after crystallization；The drying sample that crystallization obtains is roasted under oxygen-enriched state
It burns, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, when constant temperature calcining
Between be 8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature
Stirring 2 hours divides after constant temperature and is filtered, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Program liter
Temperature roasts molecular sieve 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Take second of ammonium of 100g
Molecular sieve after exchange is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C,
It is filtered and is dried after constant temperature；Molecular sieve after above-mentioned drying is added in hydrothermal treatment device, in gauge pressure
0.20MPa, 530 DEG C of temperature obtain molecular sieve to molecular sieve progress hydro-thermal process under the conditions of the 2.0 hours time of processing；Sample is compiled
Number LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3, molecular sieve are prepared using the method for embodiment 1 in CN201510147788.3
Matter is listed in table 1.
The property of 1 Y type molecular sieve of table
| Product number | 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/Al2O3Molar ratio | 48.6 | 28.6 | 33.5 | 17.3 |
| Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts 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
| Product number | 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/Al2O3Molar ratio | 7.5 | 33.5 | 8.6 |
| Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts 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 |
By 44.4 grams of LAY-1 molecular sieves (butt 90wt%), 228.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surfaces
Product 400m2/ g, butt 70wt%), 171.4 grams of peptizing agents (4g nitric acid/100g peptizing agent) be put into mixed grind in roller, be rolled into
Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier GDS-1.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4
Hour, catalyst FC-1 is obtained, 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 surfaces
Product 400m2/ g, butt 70wt%), 184.1 grams of peptizing agents (4g nitric acid/100g peptizing agent) be put into mixed grind in roller, be rolled into
Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier GDS-2.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4
Hour, catalyst FC-2 is obtained, 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 surfaces
Product 400m2/ g, butt 70wt%), 168.8 grams of peptizing agents (4g nitric acid/100g peptizing agent) be put into mixed grind in roller, be rolled into
Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier GDS-3.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4
Hour, catalyst FC-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 8
By 111.1 grams of LAY-4 molecular sieves (butt 90wt%), (pore volume 1.0mL/g compares table to 142.9 grams of macroporous aluminium oxides
Area 400m2/ g, butt 70wt%), 190.4 grams of peptizing agents (4g nitric acid/100g peptizing agent) be put into mixed grind in roller, roll
At paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier GDS-4.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4
Hour, catalyst FC-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 4 ~ 6
According to the method for embodiment 6, change LAY-2 into LDAY-1, LDAY-2, LDAY-3 respectively, be made carrier DGDS-1,
DGDS-2, DGDS-3 and catalyst DFC-1, DFC-2, DFC-3, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 9 ~ 12
This embodiment describes the Activity evaluations of catalyst FC-1, FC-2, FC-3 and FC-4 of the present invention.In fixed bed
It is evaluated on hydrogenation test apparatus, evaluation condition are as follows: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700:1, volume is empty when liquid
Fast 2.0h-1, use 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 the Activity evaluation of comparative example catalyst DFC-1, DFC-2, DFC-3 of the present invention.Solid
It is evaluated on fixed bed hydrogenation test apparatus, evaluation condition are as follows: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700:1, body when liquid
Product air speed 2.0h-1, use catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 3, and evaluation result is listed in table 4.
The composition and physico-chemical property of 2 catalyst carrier of table and catalyst
| Carrier composition and property | ||||
| Number | GDS-1 | GDS-2 | GDS-3 | GDS-4 |
| Composition | ||||
| Modified Zeolite Y, |
20 | 40 | 15 | 35 |
| Aluminium 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 composition and property | ||||
| Number | 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 composition and property | |||
| Number | DGDS-1 | DGDS-2 | DGDS-3 |
| Composition | |||
| Modified Zeolite Y, |
40 | 40 | 40 |
| Aluminium 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 composition and property | |||
| Number | 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 |
3 raw material oil nature of table
| Feedstock oil | MIP catalytic diesel oil |
| 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, |
5 |
| Sulphur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | <20.0 |
| C, wt% | 88.49 |
| H, wt% | 11.04 |
4 catalyst performance comparative evaluation's result of table
| Catalyst | FC-1 | FC-2 | FC-3 | FC-4 |
| Feedstock oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil |
| Operating condition | ||||
| Volume space velocity when 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/ |
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 oil | MIP catalytic diesel oil | MIP catalytic diesel oil |
| Operating condition | |||
| Volume space velocity when 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
It is superior to reference catalyst.
Claims (28)
1. a kind of catalyst for hydro-upgrading includes hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and oxygen
Change aluminium, wherein the property of Modified Zeolite Y is as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3Molar ratio be 10 ~
50, cell parameter be 2.436 ~ 2.445nm, total pore volume be 0.55 ~ 1.0mL/g, mesoporous pore volume account for the 70% of total pore volume with
On.
2. catalyst described in accordance with the claim 1, it is characterised in that: the property of the Y type molecular sieve is as follows: SiO2/Al2O3
Molar 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. catalyst described in accordance with the claim 1, it is characterised in that: the grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm.
4. catalyst described in accordance with the claim 1, it is characterised in that: the grain size of the Y type molecular sieve is 1.2 ~ 1.8 μm.
5. catalyst described in accordance with the claim 1, it is characterised in that: the mesoporous bore dia of the Y type molecular sieve be 2nm ~
10nm。
6. catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the Y type molecular sieve is 650m2/g~
1000m2/g。
7. catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the Y type molecular sieve is 750m2/g~
1000m2/g。
8. catalyst described in accordance with the claim 1, it is characterised in that: the infrared total acid content of the Y type molecular sieve be 0.5 ~
1.0 mmol/g。
9. catalyst described in accordance with the claim 1, it is characterised in that: in the Y type molecular sieve, Na2The weight content of O is
0.15wt% or less.
10. catalyst described in accordance with the claim 1, it is characterised in that: the property of the catalyst for hydro-upgrading is as follows: comparing table
Area is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
11. catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation active metals are group VIB and the
The metal of VIII group, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；With the weight of catalyst
On the basis of, content of the vib metals in terms of oxide is 15.0% ~ 30.0%, content of the group VIII metal in terms of oxide
It is 5.0% ~ 8.0%, the content of carrier is 62.0% ~ 80.0%.
12. according to catalyst described in claim 1 or 11, it is characterised in that: the catalyst for hydro-upgrading carrier, to carry
On the basis of the weight of body, the content of Modified Zeolite Y is 5% ~ 40%, and the content of aluminium oxide is 60% ~ 95%.
13. according to catalyst described in claim 1 or 11, it is characterised in that: the catalyst for hydro-upgrading carrier, to carry
On the basis of the weight of body, the content of Modified Zeolite Y is 10% ~ 35%, and the content of aluminium oxide is 65% ~ 90%.
14. the preparation method of any catalyst of claim 1 ~ 13, preparation and load hydrogenation active metals including carrier
Component, wherein the preparation process of carrier is as follows: Modified Zeolite Y, aluminium oxide being mixed, molding, then dry and roasting, system
At catalyst carrier, wherein the preparation method of Modified Zeolite Y, includes the following steps:
(1) NaY type molecular sieve and (NH4)2SiF6Aqueous solution contact is reacted, and is filtered and is dried after reaction；
(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure is 0.05 ~ 0.20MPa, temperature
Degree is 400 ~ 600 DEG C, and the processing time is 0.5 ~ 5.0 hour；
(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, is then passed through
Filtering and drying；
(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, Modified Zeolite Y is made.
15. according to claim 14 the method, it is characterised in that: in step (2), hydrothermal conditions are as follows: gauge pressure is
0.05 ~ 0.20MPa, temperature are 450 ~ 600 DEG C, and the processing time is 1.0 ~ 3.0 hours.
16. according to claim 14 the method, it is characterised in that: in step (1), the property of NaY type molecular sieve is as follows:
SiO2/Al2O3Molar ratio is 3 ~ 6, and grain size is 1.0 ~ 2.5 μm, and relative crystallinity is 80% ~ 110%, and cell parameter is
2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, and specific surface area is 600 ~ 900m2/ g, total pore volume are
0.3 ~ 0.4mL/g, micropore pore volume account for 75% of total pore volume or more.
17. according to claim 16 the method, it is characterised in that: in step (1), the property of NaY type molecular sieve is as follows: crystal grain
Degree is 1.2 ~ 1.8 μm.
18. according to claim 14 the method, it is characterised in that: in step (1), (NH4)2SiF6Additional amount be NaY type point
5wt% ~ 20wt% of son sieve dry weight.
19. according to claim 14 the method, it is characterised in that: in step (1), (NH4)2SiF6The mass concentration of aqueous solution
For 50 ~ 100g/L.
20. according to claim 14 the method, it is characterised in that: in step (1), NaY type molecular sieve and (NH4)2SiF6It is water-soluble
Liquid contacts the reaction condition reacted: temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour.
21. according to claim 14 the method, it is characterised in that: in step (1), NaY type molecular sieve and (NH4)2SiF6It is water-soluble
The reaction condition that liquid contact is reacted is as follows: temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
22. according to claim 14 the method, it is characterised in that: in step (1), dry condition is done at 50 ~ 95 DEG C
Dry 0.5 ~ 5.0 hour, the butt of resulting Y type molecular sieve was 60wt% ~ 80wt% after drying.
23. according to claim 14 the method, it is characterised in that: in step (3), organic formwork agent is tetraethyl hydroxide
One or more of ammonium, tetramethylammonium hydroxide, tetrapropylammonium hydroxide.
24. according to claim 14 the method, it is characterised in that: by Y type molecular sieve obtained in step (2) and organic formwork
Agent after evenly mixing, carries out hydrothermal crystallizing, and process is as follows: Y type molecular sieve obtained in step (2) is water-soluble in organic formwork agent
It is beaten in liquid, solvent and solute weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, organic formwork agent aqueous solution
Mass concentration be 3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, crystallization time
For 4 ~ 10h, gauge pressure is 0.1 ~ 0.2MPa.
25. according to claim 14 the method, it is characterised in that: step (4) be the Y type molecular sieve that obtains step (3) into
It is roasted under row low temperature oxygen-enriched atmosphere, wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, roasting
The burning time is 5 ~ 10h.
26. according to claim 14 the method, it is characterised in that: the aluminium oxide uses macroporous aluminium oxide, and property is such as
Under: 0.7 ~ 1.0mL/g of pore volume, 200 ~ 500m of specific surface area2/g。
27. according to claim 14 the method, it is characterised in that: the process of the catalyst for hydro-upgrading carrier preparation are as follows:
Modified Zeolite Y, aluminium oxide are mixed, then molding is dried and roasts, is prepared into carrier, the drying
3 ~ 6 hours dry at a temperature of 80 DEG C ~ 150 DEG C, roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
28. according to claim 14 the method, it is characterised in that: in the catalyst for hydro-upgrading, the load of active metal
Using infusion process, i.e., with the solution impregnated catalyst carrier containing active metal component, after dipping 100 DEG C ~ 150 DEG C dryings 1 ~
It 12 hours, is then roasted 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, catalyst for hydro-upgrading is made.
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