CN108262067A - A kind of hydrogenation catalyst and preparation method thereof - Google Patents
A kind of hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN108262067A CN108262067A CN201611263043.4A CN201611263043A CN108262067A CN 108262067 A CN108262067 A CN 108262067A CN 201611263043 A CN201611263043 A CN 201611263043A CN 108262067 A CN108262067 A CN 108262067A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
- 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 66
- 239000002253 acid Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 239000011973 solid acid Substances 0.000 claims abstract description 5
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002283 diesel fuel Substances 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
- 229930195733 hydrocarbon Natural products 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
- 238000005336 cracking 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
- 238000009826 distribution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 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
- 206010013786 Dry skin Diseases 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 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
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000006467 substitution reaction Methods 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
-
- 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
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of hydrogenation catalysts and preparation method thereof.The hydrogenation catalyst includes active metal and carrier；The active metal is group VIB and the metal of group VIII, and wherein vib metals are molybdenum and/or tungsten, and group VIII metal is cobalt and/or nickel；The carrier is made of solid acid component and unformed refractory oxides；The solid acid component is 22 molecular sieves of MCM and the mixture of Y molecular sieve；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, and radial direction anti-crushing power is more than 150N/cm.The hydrogenation catalyst can be applied to be hydrocracked, hydro-upgrading, during hydroisomerizing etc..
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 and Y molecular sieve mixture are acid constituent element and
Preparation method.
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.
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.But since heavy oil macromolecular enters MCM-
22 10 membered ring channels are restricted, if with Y molecular sieve act synergistically, step cracking can be carried out, have products scheme flexibly, work
The features such as skill condition is adjustable.
Invention content
The object of the present invention is to provide a kind of hydrogenation catalyst, in being hydrocracked, can flexibly produce heavy naphtha,
Aviation kerosine and 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 and Y molecular sieve
The mass ratio of mixture, the MCM-22 molecular sieves and the Y molecular sieve is 1：10~10：1；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, these, it is preferred to, the silica alumina ratio of the MCM-22 is 10~60, compares table
400~600m of face20.35~0.75ml/g of/g, Kong Rongwei；The Y molecular sieve silica alumina ratio is 5~60, specific surface be 500~
800m20.8~1.0ml/g of/g, Kong Rongwei, cell parameter 2.430-2.450nm.
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 ratio of B acid and the L acid of the Y molecular sieve is preferably 1~10.
Hydrogenation catalyst of the present invention, these, it is preferred to, the Y molecular sieve be Hydrogen, Na+Content is less than
0.05%.
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, wherein, the unformed refractory oxides are preferably aluminium oxide and unformed
One or both of sial.
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%.
The present invention also provides a kind of preparation methods of hydrogenation catalyst, are the preparation methods of above-mentioned hydrogenation catalyst,
Include the following steps：
(1) Hydrogen MCM-22 molecular sieves hydrothermal treatment, treatment temperature are 300~700 DEG C, 1~6h of processing time；Then
Through acid processing or alkali process, acid is nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid at least one, acid concentration for 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 hydroxide
Potassium, 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) Hydrogen Y molecular sieve hydrothermal treatment, 500~600 DEG C of hydro-thermal process temperature, 3~5h of hydrothermal conditions；So
It being handled by acid, acid is at least one of nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid, and acid concentration is 0.01~1mol/L,
Sour treatment temperature is room temperature~100 DEG C, and sour processing time is 20~60min；
MCM-22 molecular sieves that (3) treated and Y molecular sieve mix with unformed refractory oxides, binding agent, extrusion aid,
Molding, then drying and roasting, is made catalyst carrier；
(4) complex solution is configured using active metal and/or auxiliary agent, incipient impregnation, dipping is carried out to catalyst carrier
Carrier afterwards is aged, is dried, is roasted to get catalyst.
Except above-mentioned infusion process, ion exchange or hetero atom isomorphous substitution supported active metals and/or auxiliary agent can also be used.
The preparation method of hydrogenation catalyst of the present invention, these, it is preferred to, the temperature of the ageing is room temperature,
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 is 400~600
DEG C, the time is 3~8h.
The hydrogenation catalyst of the present invention can be applied to be hydrocracked, in the reaction of hydro-upgrading and hydroisomerizing.It is preferred anti-
The condition is answered to be：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：
Catalyst carrier for hydrgenating in the present invention, in being hydrocracked, can flexibly produce heavy naphtha, aviation kerosine and
Diesel 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 50g.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 40min is carried out to molecular sieve using the oxalic acid solution 500ml of 0.5mol/L at room temperature.100 DEG C of dry 4h,
550 DEG C of roasting 3h are to get modified molecular screen M1.
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 4h.Processing 20min is carried out to molecular sieve using the citric acid solution 400ml of 1mol/L at room temperature.100 DEG C of dry 4h,
500 DEG C of roasting 4h are to get modified molecular screen M2.
Embodiment 3
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 1h.Processing 60min is carried out to molecular sieve using the sodium hydroxide solution 500ml of 0.01mol/L at room temperature.120 DEG C dry
Dry 3h, 550 DEG C of roasting 4h are to get modified molecular screen M3.
Embodiment 4
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 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.
Embodiment 5
Weigh HY molecular sieves 50g.In high temperature furnace, steam treatment is passed through, 500 DEG C for the treatment of furnace is kept, at hydro-thermal
Manage 4h.Processing 60min is carried out to molecular sieve at 100 DEG C using the oxalic acid solution 500ml of 0.01mol/L.100 DEG C of dry 4h,
550 DEG C of roasting 4h are to get modified molecular screen Y1.
Embodiment 6
Weigh HY molecular sieves 50g.In high temperature furnace, steam treatment is passed through, 600 DEG C for the treatment of furnace is kept, at hydro-thermal
Manage 5h.Processing 20min is carried out to molecular sieve using the citric acid solution 500ml of 1mol/L at room temperature.100 DEG C of dry 4h, 550 DEG C
4h is roasted to get modified molecular screen Y2.
Embodiment 7
Weigh HY molecular sieves 50g.In high temperature furnace, steam treatment is passed through, 550 DEG C for the treatment of furnace is kept, at hydro-thermal
Manage 3h.Processing 60min is carried out to molecular sieve using the acetic acid solution 500ml of 0.5mol/L at room temperature.100 DEG C of dry 4h, 550 DEG C
4h is roasted to get modified molecular screen Y3.
Embodiment 8
M1 molecular sieve 1g, Y1 molecular sieves 10g, amorphous silicon aluminium 45g, macroporous aluminium oxide 24g and small porous aluminum oxide 20g are taken,
The nitric acid 4g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding is in 120 DEG C of dry 4h, 550 DEG C
4h is roasted to get catalyst carrier for hydrgenating S1.
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
C1。
Embodiment 9
M2 molecular sieve 5g, Y2 molecular sieves 30g, amorphous silicon aluminium 25g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken,
The nitric acid 4g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding is in 120 DEG C of dry 4h, 550 DEG C
4h is roasted to get catalyst carrier for hydrgenating S2.
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
C2。
Embodiment 10
M3 molecular sieve 30g, Y3 molecular sieves 5g, amorphous silicon aluminium 25g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken,
The nitric acid 4g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding is in 100 DEG C of dry 4h, 550 DEG C
4h is roasted to get catalyst carrier for hydrgenating S3.
Obtained carrier 100g is weighed, by 26.5g 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
C3。
Embodiment 11
M4 molecular sieve 50g, Y3 molecular sieves 10g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% nitric acid 3g carries out kneading and compacting.For catalyst carrier after molding in 100 DEG C of dry 4h, 550 DEG C roast 3h to get adding
Hydrogen catalyst carrier S 4.
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
C4。
Embodiment 12
M2 molecular sieve 20g, Y3 molecular sieves 20g, amorphous silicon aluminium 20g, macroporous aluminium oxide 15g and small porous aluminum oxide 15g are taken,
The nitric acid 4g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding is in 120 DEG C of dry 4h, 550 DEG C
4h is roasted to get catalyst carrier for hydrgenating S5.
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
C5。
Embodiment 13
M3 molecular sieve 30g, Y3 molecular sieves 3g, macroporous aluminium oxide 47g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% nitric acid 3g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 550 DEG C roast 4h to get adding
Hydrogen catalyst carrier S 6.
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
C6。
Embodiment 14
M4 molecular sieve 50g, Y2 molecular sieves 15g, macroporous aluminium oxide 15g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% nitric acid 4g carries out kneading and compacting.For catalyst carrier after molding in 120 DEG C of dry 4h, 550 DEG C roast 4h to get adding
Hydrogen catalyst carrier S 7.
Obtained carrier 100g is weighed, by 26.5g 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。
Physical data by the modified MCM-22 of embodiment 1-7 and Y molecular sieve is as shown in table 1.
The physical data of 1 modified MCM-22 of table and Y molecular sieve
| Silica alumina ratio | Specific surface m2/g | Hole holds ml/g | CB/CL | Strong acid % | Cell parameter | |
| M1 | 20 | 526.6 | 0.52 | 6.92 | 55.3 | / |
| M2 | 26 | 514.2 | 0.64 | 7.33 | 61.2 | / |
| M3 | 37 | 413.9 | 0.71 | 5.64 | 50.5 | / |
| M4 | 13 | 421.6 | 0.49 | 3.68 | 61.0 | / |
| Y1 | 9 | 612.3 | 0.81 | 4.69 | 68.0 | 2.431 |
| Y2 | 21 | 712.4 | 0.92 | 6.77 | 59.2 | 2.442 |
| Y3 | 13 | 699.6 | 0.87 | 5.49 | 50.2 | 2.436 |
2 are shown in Table as the physical property of the catalyst prepared by embodiment 8-14.
The physical property of 2 prepared catalyst of table
Embodiment 15
A kind of prepared catalyst C4, C6, C7 be applied to decompressed wax oil and catalytic diesel oil mixed raw material plus hydrogen is anti-
Ying Zhong.Table 3 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 4.
The raw material oil nature that table 3 uses
4 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 (10)
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 is the mixture of MCM-22 molecular sieves and Y molecular sieve,
The mass ratio of the MCM-22 molecular sieves and the Y molecular sieve is 1：10~10：1；The specific surface of the hydrogenation catalyst for 200~
320m2/ g, total pore volume are 0.30~0.50ml/g, 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 the silica alumina ratio of the MCM-22 is 10~60, ratio
400~600m of surface20.35~0.75ml/g of/g, Kong Rongwei；The Y molecular sieve silica alumina ratio is 5~60, specific surface be 500~
800m20.8~1.0ml/g of/g, Kong Rongwei, cell parameter are 2.430~2.450nm.
3. hydrogenation catalyst according to claim 1, which is characterized in that the strong acid ratio of the MCM-22 molecular sieves is more than
Equal to 50%.
4. 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.
5. hydrogenation catalyst according to claim 1, which is characterized in that the ratio of B acid and the L acid of the Y molecular sieve is 1
~10.
6. 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%.
7. hydrogenation catalyst according to claim 1, which is characterized in that the unformed refractory oxides for aluminium oxide and
One or both of amorphous silicon aluminium.
8. 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%.
9. a kind of preparation method of hydrogenation catalyst is the preparation side of claim 1-8 any one of them hydrogenation catalysts
Method, which is characterized in that include the following steps：
(1) Hydrogen MCM-22 molecular sieves hydrothermal treatment, treatment temperature are 300~700 DEG C, 1~6h of processing time；Then through acid
Processing or alkali process, acid are at least one of nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid, and 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, concentration
For 0.01~1mol/L, alkali purification temp is room temperature~100 DEG C, and the alkali process time is 20~60min；
(2) Hydrogen Y molecular sieve hydrothermal treatment, 500~600 DEG C of hydro-thermal process temperature, 3~5h of hydrothermal conditions；Then it passes through
Acid processing, for acid at least one of for nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid, acid concentration is 0.01~1mol/L, at acid
Reason temperature is room temperature~100 DEG C, and sour processing time is 20~60min；
(3) MCM-22 molecular sieves that treated and Y molecular sieve mix with unformed refractory oxides, binding agent, extrusion aid, into
Type, then drying and roasting, is made catalyst carrier；
(4) complex solution is configured using active metal and/or auxiliary agent, carries out incipient impregnation to catalyst carrier, after dipping
Carrier is aged, is dried, is roasted to get catalyst.
10. the preparation method of hydrogenation catalyst according to claim 9, which is characterized in 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.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532307A (en) * | 2022-09-28 | 2022-12-30 | 河北工业大学 | Hierarchical pore molecular sieve loaded metal oxide composite material and preparation method and application thereof |
| TWI829749B (en) * | 2018-10-26 | 2024-01-21 | 大陸商中國石油化工科技開發有限公司 | Phosphorus-containing high silicon molecular sieve and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393521A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Catalyst for hydrocracking medium oil and its preparing process |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103059985A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Middle-pressure hydrocracking method for producing aviation kerosene and low-freezing point diesel |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611263043.4A patent/CN108262067A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393521A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Catalyst for hydrocracking medium oil and its preparing process |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103059985A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Middle-pressure hydrocracking method for producing aviation kerosene and low-freezing point diesel |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《化工百科全书》编辑委员会编: "《化工百科全书 第4卷 发光材料-氟》", 30 September 1993, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI829749B (en) * | 2018-10-26 | 2024-01-21 | 大陸商中國石油化工科技開發有限公司 | Phosphorus-containing high silicon molecular sieve and its preparation method and application |
| CN115532307A (en) * | 2022-09-28 | 2022-12-30 | 河北工业大学 | Hierarchical pore molecular sieve loaded metal oxide composite material and preparation method and application thereof |
| CN115532307B (en) * | 2022-09-28 | 2023-09-01 | 河北工业大学 | Hierarchical porous molecular sieve supported metal oxide composite material and preparation method and application thereof |
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