CN108262063A - Hydrogenation catalyst and preparation method thereof - Google Patents
Hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN108262063A CN108262063A CN201611260811.0A CN201611260811A CN108262063A CN 108262063 A CN108262063 A CN 108262063A CN 201611260811 A CN201611260811 A CN 201611260811A CN 108262063 A CN108262063 A CN 108262063A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 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 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011973 solid acid Substances 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polycyclic hydrocarbon Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000008161 low-grade oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DGUKXCVHOUQPPA-UHFFFAOYSA-N phosphoric acid tungsten Chemical compound [W].OP(O)(O)=O DGUKXCVHOUQPPA-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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)
Abstract
The invention relates to a hydrogenation catalyst and a preparation method thereof. The catalyst comprises an active metal and a carrier; the active metal is metal of VIB group and VIII group, wherein the metal of VIB group is molybdenum and/or tungsten, and the metal of VIII group is cobalt and/or nickel; the carrier consists of a solid acid component and an amorphous heat-resistant oxide; the solid acid component is an MCM-22 molecular sieve, the silica-alumina ratio of the molecular sieve is 10-50, and the specific surface area is 400-700 m2The pore volume is 0.35-0.75 ml/g; the specific surface of the hydrogenation catalyst is 200-320 m2the hydrogenation catalyst has the advantages of a total pore volume of 0.30-0.50 ml/g, an infrared acid content of 0.50-1.0 mmol/g, a ratio of B acid to L acid of 0.2-1.0, and a radial crushing resistance of more than 150N/cm., and can be applied to hydrocracking, hydrogenation modification, hydroisomerization and other processes.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and preparation method thereof, specifically a kind of to be applied to be hydrocracked, add
Hydrogen modify and the processes such as hydroisomerizing by hydrogenation catalyst that MCM-22 molecular sieves are acid constituent element and preparation method thereof.
Background technology
Important manufacturing process of the hydrocracking technology as heavy oil lighting, low grade oils modification and Integrated Refinery And Petrochemical, tool
Have the advantages that production decision is flexible, adaptability to raw material is strong, purpose product selectivity is high, high-quality and tail oil added value is high.Add hydrogen
Cracking catalyst is the core of hydrocracking technology, therefore development, the development and application of hydrocracking catalyst are also that hydrogen is added to split
Change the main contents of technological progress.Hydrocracking catalyst is typical bifunctional catalyst, and catalyst carrier material offer is split
Change function, open loop is substantially carried out on acidic site, n-alkane is hydrocracked, the de- reactions such as alkyl, isomerization.At present, for
The active metal component understanding of the mechanism of action and its load technology of preparing on a support material in hydrocracking catalyst show
It has been mature on the whole with perfect, and the novel carriers material with more dominance energy also just becomes grinding for hydrocracking catalyst technology
Heat generating spot.
VGO feedstock is mainly made of saturated hydrocarbons, aromatic hydrocarbons and colloid etc..The polycyclic cyclic hydrocarbon molecules for making diameter big are with urging
Change activated centre contact, it is necessary that catalyst has good pore structure.Hydrocracking catalyst only have big aperture,
Macropore holds, pore size distribution is uniform, pore system is open and the pore structures feature such as unimpeded, and the polycyclic hydrocarbon molecule that can just make diameter big compares
Catalyst duct is easily accessible, increases the chance for contacting and reacting with activated centre, improves ring-opening reaction speed；Diameter is small
Chain hydrocarbon can then be easier to be detached from from duct, diffuse out, and reduce chain-breaking reaction speed.The acidity and pore structure of catalysis material
It is the principal element for determining hydrocracking catalyst.
Y types and Beta types molecular sieve are due to twelve-ring macroporous structure, being widely used in hydrocracking catalyst
As acid centre.Y type molecular sieve has the characteristics that three-dimensional supercage, tetrahedron trend and twelve-ring macroporous structure, has higher
Segmented ring performance, mostly suitable for light oil type hydrogen cracking catalyst.Beta type molecular sieves are twelve-ring macropore straight channels
Structure, it is preferable for straight-chain hydrocarbons stereoselectivity, mostly suitable in middle oil type hydrocracking catalyst.In recent years, gasoline demand
Steady-state growth is measured, the growth of diesel oil demand is slower, and the development of diesel oil substitute fuel technology, diesel and gasoline ratio persistently reduce in addition, it is contemplated that
The year two thousand twenty is down to 1.0 or so.And aviation kerosine was increased speed very fast in recent years, annual growth 9.7%.In addition, ethylene and virtue
Hydrocarbon demand sustainable growth, but the deficiency of the raw material degree of self-sufficiency limits its development.Changed according to diesel and gasoline ratio, mobile type, which is hydrocracked, urges
The exploitation of agent has great importance.MCM-22 molecular sieves have MWW structures, there is unique 10 membered ring channel and 12 yuan of annular distances
Cave structure shows good catalytic performance in the reactions such as alkylation, toluene disproportionation, xylene isomerization.Due to MCM-
22 unique composite constructions, the distribution of special acid site and excellent hydrothermal stability, can be applied in hydrocracking catalyst,
Have the characteristics that products scheme is flexible, process conditions are adjustable.
CN201511028094.4 discloses a kind of high-precision desulphurization and denitrification catalyst carrier, by MCM-22 molecular sieves and oxidation
Magnesium, Si oxide and aluminum oxide are mixed with and obtain.Load C o, Mo, Ni, W metal, using naphtha as raw material, in 250-350
Prepared catalyst is evaluated under the conditions of DEG C, as a result shows prepared catalyst desulfurizing rate up to more than 92%, denitrogenation
Rate is horizontal higher than the desulfurization removing nitric of contrast medium up to more than 35%.
CN200910012945.4 discloses a kind of metal supported MCM-22 molecular sieve hollow sphere bifunctional catalyst system
Preparation Method using MCM-22 as the supported on carriers metal Mo of acid constituent element, for oxygen-free dehydrogenating aromatization of methane aromatic hydrocarbons, has
Methane conversion is high, has strong anti-carbon capacity, the features such as service life is long.
CN201510830592.4 discloses a kind of catalyst using the MCM-22 that Zn is modified as main acid constituent element and carries
The catalyst of phosphoric acid tungsten is loaded on body.Catalyst is applied in long chain alkylphenol catalysis reaction, has catalyst stabilization, service life
Length obtains the features such as product acid value is low, dealkylation rate is low, solves industry at present using difficult existing for ion exchange resin
Topic.
Due to the unique composite constructions of MCM-22, the distribution of special acid site and excellent hydrothermal stability, can be applied to
In hydrocracking catalyst, have the characteristics that products scheme is flexible, process conditions are adjustable.Using MCM-22 as the load of acid constituent element
Type catalyst, applied to be hydrocracked, not disclosed and report in the reactions such as hydroisomerizing and hydro-upgrading.
Invention content
The object of the present invention is to provide a kind of hydrogenation catalyst, which is applied in being hydrocracked, and can flexibly produce
Heavy naphtha, aviation kerosine or diesel oil.
For this purpose, the present invention provides a kind of hydrogenation catalyst, including active metal and carrier；The active metal is Section VI B
Race and the metal of group VIII, wherein vib metals are molybdenum and/or tungsten, and group VIII metal is cobalt and/or nickel；The load
Body is made of solid acid component and unformed refractory oxides；The solid acid component is MCM-22 molecular sieves, the molecular sieve
Silica alumina ratio is 10~50, and specific surface is 400~700m20.35~0.75ml/g of/g, Kong Rongwei；The specific surface of the hydrogenation catalyst
For 200~320m2/ g, total pore volume are the ratio of 0.30~0.50ml/g, meleic acid amount 0.50~1.0mmol/g, B acid and L acid
It is 0.2~1.0, radial direction anti-crushing power is more than 150N/cm.
Hydrogenation catalyst of the present invention, wherein, on the basis of catalyst, the vib metals are in terms of oxide
Content be preferably 10~30wt%, content of the group VIII metal in terms of oxide is preferably 3~10wt%.
Hydrogenation catalyst of the present invention, these, it is preferred to, which further includes auxiliary agent, and the auxiliary agent is F, B
One or both of with P, on the basis of catalyst, the content of the auxiliary agent is 0.1~5wt%.
Hydrogenation catalyst of the present invention, wherein, on the basis of carrier, the content of the solid acid component is preferably 10
~80wt%, the content of the unformed refractory oxides is preferably 20~90wt%.
Hydrogenation catalyst of the present invention, these, it is preferred to, the X-ray diffraction peak position of the MCM-22 molecular sieves
It puts respectively at 3.1 °, 6.5 °, 7.1 °, 9.7 °, 26.1 °.
Hydrogenation catalyst of the present invention, wherein, the B acid of the MCM-22 molecular sieves and the ratio of L acid is preferably 1~
10, more preferable strong acid ratio >=50%.
Hydrogenation catalyst of the present invention, wherein, the unformed refractory oxides are preferably aluminium oxide and unformed
At least one of sial.
The present invention also provides a kind of preparation methods of hydrogenation catalyst, are the preparation methods of above-mentioned hydrogenation catalyst,
It is characterised in that it includes following steps：
(1) it is molecular sieve modified：Hydrothermal treatment, treatment temperature are 500~600 DEG C, 1~6h of processing time, preferred process
3~5h of time；Then it is sour at least one of nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid, acid through acid processing or alkali process
A concentration of 0.01~1mol/L, sour treatment temperature are room temperature~100 DEG C, and sour processing time is 20~60min；Alkali is sodium hydroxide
And/or potassium hydroxide, a concentration of 0.01~1mol/L, alkali purification temp are room temperature~100 DEG C, the alkali process time for 20~
60min；
(2) modified molecular sieve is mixed with unformed refractory oxides, binding agent, extrusion aid, is molded, then dry roasting
It burns, catalyst carrier is made；
(3) catalyst carrier by infusion process, ion exchange or hetero atom isomorphous substitution supported active metals and/or helps
Then agent is aged, is dried, is roasted to get catalyst.
The preparation method of hydrogenation catalyst of the present invention, in step (3), the step of infusion process, is preferably：It adopts
With active metal and/or auxiliary agent configuration complex solution, incipient impregnation is carried out to catalyst carrier.
The preparation method of hydrogenation catalyst of the present invention, in step (3), it is preferred that the temperature of the ageing is
Room temperature, time are 1~8h；The temperature of the drying is 100~150 DEG C, and the time is 3~8h；The temperature of the roasting for 400~
600 DEG C, the time is 3~8h.
Hydrogenation catalyst prepared by the present invention can be applied to be hydrocracked, in the reaction of hydro-upgrading and hydroisomerizing.It is preferred that
Reaction condition is：300~400 DEG C, 6~18MPa of reaction pressure of reaction temperature, hydrogen to oil volume ratio 500~1500, volume space velocity
0.5~2.5h-1。
Beneficial effects of the present invention：
Hydrogenation catalyst in the present invention in being hydrocracked, can flexibly produce heavy naphtha, aviation kerosine and bavin
Oil has that products scheme is flexible, and process conditions are adjustable and the features such as good product quality.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
Embodiment 1
Weigh MCM-22 molecular sieves 20g.In high temperature furnace, steam treatment is passed through, keeps 550 DEG C for the treatment of furnace, water
It is heat-treated 4h.Processing 60min is carried out to molecular sieve using the oxalic acid solution 200ml of 1mol/L at room temperature.100 DEG C of dry 4h, 550
DEG C roasting 4h to get modified molecular screen M1.
M1 modified molecular screens 10g, amorphous silicon aluminium 50g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken, adds in quality
A concentration of 65% nitric acid 4g carries out kneading and compacting.Molecular sieve, amorphous silicon aluminium, macroporous aluminium oxide and small porous aluminum oxide with
Butt is remembered.For catalyst carrier after molding in 120 DEG C of dry 4h, 550 DEG C roast 4h to get catalyst carrier for hydrgenating S1.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 2h, 120 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C1。
Embodiment 2
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 600 DEG C for the treatment of furnace, water
It is heat-treated 1h.Processing 50min is carried out to molecular sieve using the citric acid solution 400ml of 1mol/L at room temperature.100 DEG C of dry 4h,
550 DEG C of roasting 4h are to get modified molecular screen M2.
M2 modified molecular screens 30g, macroporous aluminium oxide 50g and small porous aluminum oxide 20g add in the nitric acid that mass concentration is 65%
4g carries out kneading and compacting.Catalyst carrier after molding is carried in 120 DEG C of dry 4h, 600 DEG C of roasting 4h to get hydrogenation catalyst
Body S2.
Obtained carrier 100g is weighed, by 25.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 120 DEG C of dry 4h, then 500 DEG C of roasting 4h in Muffle furnace, catalyst is made
C2。
Embodiment 3
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 300 DEG C for the treatment of furnace, water
It is heat-treated 6h.Processing 50min is carried out to molecular sieve using the citric acid solution 400ml of 1mol/L at room temperature.100 DEG C of dry 4h,
550 DEG C of roasting 4h are to get modified molecular screen M3.
M3 modified molecular screens 30g, amorphous silicon aluminium 20g, macroporous aluminium oxide 30g and small porous aluminum oxide 20g are taken, adds in quality
A concentration of 65% nitric acid 4g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 600 DEG C roast 4h,
Up to catalyst carrier for hydrgenating S3.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C3。
Embodiment 4
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 3h.Processing 50min is carried out to molecular sieve using the sodium hydroxide solution 400ml of 1mol/L at room temperature.100 DEG C of dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen M4.
M4 modified molecular screens are taken treated molecular sieve 50g, macroporous aluminium oxide 30g and small porous aluminum oxide 20g, add in quality
A concentration of 65% nitric acid 3g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 600 DEG C roast 4h,
Up to catalyst carrier for hydrgenating S4.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 30.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C4。
Embodiment 5
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 3h.Processing 50min is carried out to molecular sieve using the sodium hydroxide solution 400ml of 1mol/L at room temperature.100 DEG C of dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen M5.
M5 modified molecular screens 70g, macroporous aluminium oxide 20g and small porous aluminum oxide 10g are taken, adds in the nitre that mass concentration is 65%
Sour 4g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Carrier S 5.
Obtained carrier 100g is weighed, by 25.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C5。
Embodiment 6
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 700 DEG C for the treatment of furnace, water
It is heat-treated 3h.Processing 50min is carried out to molecular sieve using the sodium hydroxide solution 400ml of 1mol/L at room temperature.100 DEG C of dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen M6.
M6 modified molecular screens 70g, macroporous aluminium oxide 20g and small porous aluminum oxide 10g are taken, adds in the nitre that mass concentration is 65%
Sour 4g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Carrier S 6.
Obtained carrier 100g is weighed, by 26.5g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C6。
Embodiment 7
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 2h.Processing 50min is carried out to molecular sieve using the salpeter solution 500ml of 0.2mol/L at room temperature.100 DEG C of dry 4h,
550 DEG C of roasting 4h are to get modified molecular screen M7.
M7 modified molecular screens 60g, macroporous aluminium oxide 30g and small porous aluminum oxide 10g are taken, adds in the nitre that mass concentration is 65%
Sour 3g carries out kneading and compacting.For catalyst carrier after molding in 100 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Carrier S 7.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.5g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C7。
Embodiment 8
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 2h.Using the oxalic acid of 0.2mol/L, acetic acid 1:1 complex solution 500ml carries out processing 50min to molecular sieve at room temperature.
100 DEG C of dry 4h, 550 DEG C of roasting 4h are to get modified molecular screen M8.
M8 modified molecular screens 60g, macroporous aluminium oxide 30g and small porous aluminum oxide 10g are taken, adds in the nitre that mass concentration is 65%
Sour 4g carries out kneading and compacting.For catalyst carrier after molding in 100 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Carrier S 8.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C8。
Embodiment 9
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 4h.50min is handled to molecular sieve at 60 DEG C using the potassium hydroxide solution 500ml of 0.2mol/L.100 DEG C of dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen M9.
M9 modified molecular screens 80g, macroporous aluminium oxide 10g and small porous aluminum oxide 10g are taken, adds in the nitre that mass concentration is 65%
Sour 4g carries out kneading and compacting.For catalyst carrier after molding in 100 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Carrier S 9.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C9。
Embodiment 10
Weigh MCM-22 molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace, water
It is heat-treated 4h.50min is handled to molecular sieve at 60 DEG C using the potassium hydroxide solution 500ml of 0.2mol/L.100 DEG C of dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen M10.
M10 modified molecular screens 80g, macroporous aluminium oxide 10g and small porous aluminum oxide 10g are taken, it is 65% to add in mass concentration
Nitric acid 3g carries out kneading and compacting.For catalyst carrier after molding in 100 DEG C of dry 4h, 600 DEG C roast 4h to get hydrogenation catalyst
Agent carrier S10.
Obtained carrier 100g is weighed, by 26.0g nickel nitrates and 31.0g ammonium metatungstates are soluble in water is configured to metal salt
Solution carries out incipient impregnation.During ageing 4h, 100 DEG C of dry 4h, then 550 DEG C of roasting 4h in Muffle furnace, catalyst is made
C10。
As prepared by above-described embodiment series modified molecular sieve, the physical property of catalyst carrier and catalyst is shown in Table respectively
1st, table 2 and table 3.
The physical property of 1 modified MCM-22 molecular sieves of table
The physical property of serial carrier prepared by table 2
The physical property of catalyst series prepared by table 3
Embodiment 11
Prepared catalyst C3, C5, C9 are applied in the hydrogenation reaction of decompressed wax oil and catalytic diesel oil mixed raw material.
Table 4 gives the property of used feedstock oil.Reaction condition：380 DEG C, hydrogen partial pressure 10MPa of reaction temperature, hydrogen-oil ratio 1000:
1, air speed 1.0h-1.Evaluation result is listed in table 5.
The raw material oil nature that table 4 uses
5 evaluating catalyst result of table
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of hydrogenation catalyst, which is characterized in that including active metal and carrier；The active metal is group VIB and the
The metal of VIII group, wherein vib metals are molybdenum and/or tungsten, and group VIII metal is cobalt and/or nickel；The carrier is by solid
Body acid constituents and unformed refractory oxides composition；The solid acid component be MCM-22 molecular sieves, the silica alumina ratio of the molecular sieve
It is 10~50, specific surface is 400~700m20.35~0.75ml/g of/g, Kong Rongwei；The specific surface of the hydrogenation catalyst is 200
~320m2/ g, total pore volume are 0.30~0.50ml/g, and the ratio of meleic acid amount 0.50~1.0mmol/g, B acid and L acid is 0.2
~1.0, radial direction anti-crushing power is more than 150N/cm.
2. hydrogenation catalyst according to claim 1, which is characterized in that on the basis of catalyst, the vib metals
Using the content that oxide is counted as 10~30wt%, the group VIII metal is using the content that oxide is counted as 3~10wt%.
3. hydrogenation catalyst according to claim 1, which is characterized in that the catalyst further includes auxiliary agent, and the auxiliary agent is
F, one or both of B and P, on the basis of catalyst, the content of the auxiliary agent is 0.1~5wt%.
4. hydrogenation catalyst according to claim 1, which is characterized in that on the basis of carrier, the solid acid component
Content is 10~80wt%, and the content of the unformed refractory oxides is 20~90wt%.
5. hydrogenation catalyst according to claim 1, which is characterized in that the ratio of B acid and the L acid of the MCM-22 molecular sieves
Be worth is 1~10.
6. hydrogenation catalyst according to claim 1, which is characterized in that the unformed refractory oxides for aluminium oxide and
At least one of amorphous silicon aluminium.
7. a kind of preparation method of hydrogenation catalyst is the preparation side of claim 1~6 any one of them hydrogenation catalyst
Method, which is characterized in that include the following steps：
(1) it is molecular sieve modified：Hydrothermal treatment, treatment temperature are 500~600 DEG C, 1~6h of processing time；Then it is handled through acid
Or alkali process, acid are at least one of nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid, acid concentration is 0.01~1mol/L, sour
Treatment temperature is room temperature~100 DEG C, and sour processing time is 20~60min；Alkali be sodium hydroxide and/or potassium hydroxide, it is a concentration of
0.01~1mol/L, alkali purification temp are room temperature~100 DEG C, and the alkali process time is 20~60min；
(2) modified molecular sieve is mixed with unformed refractory oxides, binding agent, extrusion aid, is molded, then drying and roasting,
Catalyst carrier is made；
(3) catalyst carrier is by infusion process, ion exchange or hetero atom isomorphous substitution supported active metals and/or auxiliary agent, so
After be aged, dry, roast to get catalyst.
8. the preparation method of hydrogenation catalyst according to claim 7, which is characterized in that in step (3), the infusion process
The step of be：Using active metal and/or auxiliary agent configuration complex solution, incipient impregnation is carried out to catalyst carrier.
9. the preparation method of hydrogenation catalyst according to claim 7, which is characterized in that in step (3), the ageing
Temperature is room temperature, and the time is 1~8h；The temperature of the drying is 100~150 DEG C, and the time is 3~8h；The temperature of the roasting
It it is 400~600 DEG C, the time is 3~8h.
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