CN108264927A - Hydrogenation catalyst carrier and preparation method thereof - Google Patents
Hydrogenation catalyst carrier and preparation method thereof Download PDFInfo
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- CN108264927A CN108264927A CN201611258010.0A CN201611258010A CN108264927A CN 108264927 A CN108264927 A CN 108264927A CN 201611258010 A CN201611258010 A CN 201611258010A CN 108264927 A CN108264927 A CN 108264927A
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- molecular sieves
- hydrgenating
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 70
- 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 70
- 239000002253 acid Substances 0.000 claims abstract description 46
- 239000011973 solid acid Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 37
- 238000012545 processing Methods 0.000 claims description 23
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000008161 low-grade oil Substances 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polycyclic hydrocarbon Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000010998 test method 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
- 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
- B01J29/7007—Zeolite Beta
-
- 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
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a hydrogenation catalyst carrier, which comprises a solid acid component and an amorphous heat-resistant oxide, wherein the specific surface area of the hydrogenation catalyst carrier is 220-450 m2the catalyst carrier comprises the following components, by weight, 0.35-0.70 ml/g of total pore volume, 0.50-1.0 mmol/g of infrared acid, 0.2-1.0 of ratio of B acid to L acid, more than 130N/cm of radial crushing resistance, 10-80% of solid acid component and 20-90% of amorphous heat-resistant oxide, wherein the solid acid component is a mixture of an MCM-22 molecular sieve and a Beta molecular sieve, and the mixing ratio is 1: 10-10: 1.
Description
Technical field
The invention belongs to a kind of catalyst carrier for hydrgenating and preparation method, it is specifically a kind of be applied to be hydrocracked,
The processes such as hydro-upgrading and hydroisomerizing by catalyst that MCM-22 molecular sieves and Beta molecular sieve mixtures are acid constituent element
Carrier 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.
CN200680054516.8 discloses a kind of improved catalyst and preparation method thereof.The acid carrier of catalyst is
Beta molecular sieves or MWW structure molecular screens or the two mixture, catalyst are mainly used for the alkylation of aromatic hydrocarbon, have higher
Activity and selectivity.
CN200910201658.8 discloses a kind of Beta and MCM-22 Intergrown moleculars sieve catalyst, and active height is urged
The features such as agent intensity is good.
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 acted synergistically with Beta molecular sieves, can carry out step cracking, have products scheme spirit
Living, the features such as process conditions are adjustable.
Invention content
The object of the present invention is to provide a kind of catalyst carrier for hydrgenating, which is applied in being hydrocracked, and can flexibly give birth to
Produce heavy naphtha, aviation kerosine and diesel oil.
For this purpose, the present invention provides a kind of catalyst carrier for hydrgenating, including solid acid component and unformed refractory oxides,
It is characterized in that：220~450m of specific surface area of the catalyst carrier for hydrgenating2/ g, 0.35~0.70ml/g of total pore volume, meleic acid
The ratio of 0.50~1.0mmol/g of amount, B acid and L acid is 0.2~1.0, and radial direction anti-crushing power is more than 130N/cm；
On the basis of the total weight of the carrier, solid acid component content is 10~80%, and unformed refractory oxides contain
Amount 20~90%；
Wherein, mixture of the solid acid component for MCM-22 molecular sieves and Beta molecular sieves, mixed proportion 1：10
~10：1；
The silica alumina ratio of the MCM-22 molecular sieves is 10~60,400~600m of specific surface area2/ g, Kong Rongwei 0.35~
0.75ml/g；
The silica alumina ratio of the Beta molecular sieves is 30~100,300~600m of specific surface area2/ g, hole hold 0.4~0.8ml/
g。
Catalyst carrier for hydrgenating of the present invention, wherein：The B acid of the MCM-22 molecular sieves and the ratio of L acid are preferred
It is 1~10.
Catalyst carrier for hydrgenating of the present invention, wherein：The strong acid ratio of the MCM-22 molecular sieves preferably greater than etc.
In 50%.
Catalyst carrier for hydrgenating of the present invention, wherein：The B acid of the Beta molecular sieves and the ratio of L acid for 1~
10。
Catalyst carrier for hydrgenating of the present invention, wherein：The unformed refractory oxides be preferably aluminium oxide and/or
Amorphous silicon aluminium.
Catalyst carrier for hydrgenating of the present invention, wherein：The Beta molecular sieves are preferably Hydrogen, Na+Content is preferred
Less than 0.1%.
The present invention also provides a kind of preparation methods of catalyst carrier for hydrgenating, are the preparations of above-mentioned catalyst carrier for hydrgenating
Method includes the following steps：
(1) MCM-22 molecular sieves are through steam treatment, and treatment temperature is 300~700 DEG C, 1~6h of processing time；Then again
Through acid or alkali process, a concentration of 0.01~1mol/L of the acid or alkali, treatment temperature is room temperature to 100 DEG C, and processing time is
20~60min；
(2) for Beta molecular sieves through steam treatment, treatment temperature is 500~600 DEG C, and processing time is 3~5h；Then again
It is handled through acid, the acid concentration is 0.01~1mol/L, and treatment temperature is room temperature to 100 DEG C, and processing time is 20~60min；
(3) MCM-22 molecular sieves and Beta molecular sieves are mixed with unformed refractory oxides, binding agent, extrusion aid after handling
It closes, molding, then drying and roasting, is made catalyst carrier.
The preparation method of catalyst carrier for hydrgenating of the present invention, wherein：In step (1) and step (2), the acid point
Not You Xuanwei nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid one or more.
The preparation method of catalyst carrier for hydrgenating of the present invention, wherein：In step (1), the alkali is preferably hydrogen-oxygen
Change sodium and/or potassium hydroxide.
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
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The catalyst carrier for hydrgenating of the present invention, is made of solid acid component and unformed refractory oxides.Hydrogenation catalyst
220~350m of specific surface of carrier2/ g, 0.35~0.70ml/g of total pore volume, meleic acid amount 0.50~1.0mmol/g, B acid and L
The ratio of acid is 0.2~1.0, and radial direction anti-crushing power is more than 130N/cm.On the basis of the total weight of the carrier, solid acid group
It is 10~80% to divide content, unformed refractory oxides content 20~90%.
Mixture of the solid acid component for MCM-22 molecular sieves and Beta molecular sieves, mixed proportion 1 in the present invention：10~
10：1.
MCM-22 molecular sieves are loaded for Hydrogen or by infusion process, ion exchange or hetero atom isomorphous substitution in the present invention
Mo, Ni, W's is one or more.Silica alumina ratio is 10~60,400~600m of specific surface20.35~0.75ml/g of/g, Kong Rongwei.X
X ray diffraction peak position is respectively at 3.1 °, 6.5 °, 7.1 °, 9.7 °, 26.1 °.The ratio of B acid and L acid is 1~10.Strong acid ratio
Example is not less than 50%.
In the present invention Beta molecular sieves for Hydrogen or by infusion process, ion exchange or hetero atom isomorphous substitution load Mo,
Ni, W's is one or more.Beta molecular sieves silica alumina ratio 30~100,300~600m2/g of specific surface, hole hold 0.4~0.8ml/g.
Unformed refractory oxides are aluminium oxide in the present invention, the one or two kinds of of amorphous silicon aluminium mix.
The preparation method of the catalyst carrier for hydrgenating of the present invention, includes the following steps：
(1) Hydrogen MCM-22 molecular sieves are handled through water steaming, and treatment temperature is 300~700 DEG C, 1~6h of processing time.Then
Through acid processing or alkali process, acid can be the one or more of nitric acid, hydrochloric acid, citric acid, oxalic acid, acetic acid, acid concentration for 0.01~
1mol/L, treatment temperature are room temperature~100 DEG C, and processing time is 20~60min.Alkali can be sodium hydroxide, potassium hydroxide one
Kind or two kinds, a concentration of 0.01~1mol/L, treatment temperature be room temperature~100 DEG C, processing time be 20~60min.
(2) Hydrogen Beta molecular sieves hydrothermal treatment, 500~600 DEG C for the treatment of temperature, 3~5h of processing time.Then through acid
Processing, acid can be the one or more of nitric acid, hydrochloric acid, citric acid, oxalic acid, acetic acid, and acid concentration is 0.01~1mol/L, handles temperature
It spends for room temperature~100 DEG C, processing time is 20~60min.
(3) molecular sieve that treated and unformed refractory oxides, binding agent, extrusion aid mix in certain proportion, into
Type, then drying and roasting, is made catalyst carrier.
Catalyst carrier for hydrgenating in the present invention can be applied to be hydrocracked, hydro-upgrading, in hydroisomerization catalyst.
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,
550 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 Hydrogen Beta molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 500 DEG C for the treatment of furnace,
Hydro-thermal process 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 dry
Dry 4h, 550 DEG C of roasting 4h are to get modified molecular screen B1.
Embodiment 6
Weigh Hydrogen Beta molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 600 DEG C for the treatment of furnace,
Hydro-thermal process 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 dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen B2.
Embodiment 7
Weigh Hydrogen Beta molecular sieves 50g.In high temperature furnace, steam treatment is passed through, keeps 550 DEG C for the treatment of furnace,
Hydro-thermal process 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 dryings
4h, 550 DEG C of roasting 4h are to get modified molecular screen B3.
The physical data of 1 modified MCM-22 and Beta molecular sieves of table
| Silica alumina ratio | Specific surface m2/g | Hole holds ml/g | CB/CL | Strong acid % | |
| 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 |
| B1 | 43 | 472.6 | 0.52 | 5.33 | 53.1 |
| B2 | 79 | 522.8 | 0.64 | 6.72 | 66.3 |
| B3 | 55 | 513.2 | 0.59 | 6.31 | 60.1 |
Embodiment 8
M1 molecular sieve 1g, B1 molecular sieves 10g, amorphous silicon aluminium 45g, macroporous aluminium oxide 24g and small porous aluminum oxide 20g are taken,
The salpeter solution 3g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding in 120 DEG C of dry 4h,
550 DEG C of roasting 4h are to get catalyst carrier for hydrgenating S1.
Embodiment 9
M2 molecular sieve 5g, B2 molecular sieves 30g, amorphous silicon aluminium 25g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken,
The salpeter solution 3g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding in 120 DEG C of dry 4h,
550 DEG C of roasting 4h are to get catalyst carrier for hydrgenating S2.
Embodiment 10
M3 molecular sieve 30g, B3 molecular sieves 5g, amorphous silicon aluminium 25g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken,
The salpeter solution 4g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding in 100 DEG C of dry 4h,
550 DEG C of roasting 4h are to get catalyst carrier for hydrgenating S3.
Embodiment 11
M4 molecular sieve 50g, B3 molecular sieves 10g, macroporous aluminium oxide 20g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% salpeter solution 4g carries out kneading and compacting.Catalyst carrier after molding is in 100 DEG C of dry 4h, and 550 DEG C roast 3h, i.e.,
Obtain catalyst carrier for hydrgenating S4.
Embodiment 12
M2 molecular sieve 20g, B3 molecular sieves 20g, amorphous silicon aluminium 20g, macroporous aluminium oxide 15g and small porous aluminum oxide 15g are taken,
The salpeter solution 3g that mass concentration is 65% is added in, carries out kneading and compacting.Catalyst carrier after molding in 120 DEG C of dry 4h,
550 DEG C of roasting 4h are to get catalyst carrier for hydrgenating S5.
Embodiment 13
M3 molecular sieve 30g, B3 molecular sieves 3g, macroporous aluminium oxide 47g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% salpeter solution 3g carries out kneading and compacting.Catalyst carrier after molding is in 120 DEG C of dry 4h, and 550 DEG C roast 4h, i.e.,
Obtain catalyst carrier for hydrgenating S6.
Embodiment 14
M4 molecular sieve 50g, B2 molecular sieves 15g, macroporous aluminium oxide 15g and small porous aluminum oxide 20g are taken, adding in mass concentration is
65% salpeter solution 4g carries out kneading and compacting.Catalyst carrier after molding is in 120 DEG C of dry 4h, and 550 DEG C roast 4h, i.e.,
Obtain catalyst carrier for hydrgenating S7.
The physical property of prepared catalyst carrier is shown in Table 2.
The physical property of serial carrier prepared by table 2
Embodiment 15
S4, S6, S7 carrier of preparation are urged by being prepared into after the common upper metal active constituent of dipping method load
Agent C4, C6, C7, and applied to a kind of decompressed wax oil and the evaluation of the hydrocracking reaction of catalytic diesel oil mixed raw material.Table 3 provides
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
Claims (8)
1. a kind of catalyst carrier for hydrgenating, including solid acid component and unformed refractory oxides, it is characterised in that：Described plus hydrogen
220~450m of specific surface area of catalyst carrier2/ g, 0.35~0.70ml/g of total pore volume, 0.50~1.0mmol/ of meleic acid amount
The ratio of g, B acid and L acid is 0.2~1.0, and radial direction anti-crushing power is more than 130N/cm；
On the basis of the total weight of the carrier, solid acid component content is 10~80%, unformed refractory oxides content 20
~90%；
Wherein, mixture of the solid acid component for MCM-22 molecular sieves and Beta molecular sieves, mixed proportion 1：10~10：
1；
The silica alumina ratio of the MCM-22 molecular sieves is 10~60,400~600m of specific surface area20.35~0.75ml/ of/g, Kong Rongwei
g；
The silica alumina ratio of the Beta molecular sieves is 30~100,300~600m of specific surface area2/ g, hole hold 0.4~0.8ml/g.
2. catalyst carrier for hydrgenating according to claim 1, it is characterised in that：B acid and the L acid of the MCM-22 molecular sieves
Ratio be 1~10.
3. catalyst carrier for hydrgenating according to claim 1 or 2, it is characterised in that：The strong acid of the MCM-22 molecular sieves
Ratio is more than or equal to 50%.
4. catalyst carrier for hydrgenating according to claim 1 or 2, it is characterised in that：The B acid and L of the Beta molecular sieves
The ratio of acid is 1~10.
5. catalyst carrier for hydrgenating according to claim 1 or 2, it is characterised in that：The unformed refractory oxides are
Aluminium oxide and/or amorphous silicon aluminium.
6. a kind of preparation method of catalyst carrier for hydrgenating is Claims 1 to 5 any one of them catalyst carrier for hydrgenating
Preparation method, include the following steps：
(1) MCM-22 molecular sieves are through steam treatment, and treatment temperature is 300~700 DEG C, 1~6h of processing time；Then again through acid
Or alkali process, a concentration of 0.01~1mol/L of the acid or alkali, treatment temperature are room temperature to 100 DEG C, processing time for 20~
60min；
(2) for Beta molecular sieves through steam treatment, treatment temperature is 500~600 DEG C, and processing time is 3~5h；Then again through acid
Processing, the acid concentration are 0.01~1mol/L, and treatment temperature is room temperature to 100 DEG C, and processing time is 20~60min；
(3) MCM-22 molecular sieves and Beta molecular sieves are mixed with unformed refractory oxides, binding agent, extrusion aid after handling, into
Type, then drying and roasting, is made catalyst carrier.
7. the preparation method of catalyst carrier for hydrgenating according to claim 6, it is characterised in that：Step (1) and step (2)
In, the acid is respectively the one or more of nitric acid, hydrochloric acid, citric acid, oxalic acid and acetic acid.
8. the preparation method of catalyst carrier for hydrgenating according to claim 6, it is characterised in that：In step (1), the alkali
For sodium hydroxide and/or potassium hydroxide.
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| US5279726A (en) * | 1990-05-22 | 1994-01-18 | Union Oil Company Of California | Catalyst containing zeolite beta and processes for its use |
| CN1350886A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Composite zeolite and its preparing process |
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