CN107790175A - A kind of application of the preparation method of catalyst for hydrogenation de-waxing and the catalyst and the catalyst that are prepared by this method - Google Patents
A kind of application of the preparation method of catalyst for hydrogenation de-waxing and the catalyst and the catalyst that are prepared by this method Download PDFInfo
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- CN107790175A CN107790175A CN201610781997.8A CN201610781997A CN107790175A CN 107790175 A CN107790175 A CN 107790175A CN 201610781997 A CN201610781997 A CN 201610781997A CN 107790175 A CN107790175 A CN 107790175A
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- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- 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
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- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
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- 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
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- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The application of the catalyst and the catalyst that are prepared present disclose provides a kind of preparation method of catalyst for hydrogenation de-waxing and by this method, the preparation method include：A, molecular sieve inorganic oxide carrier is subjected to the first dipping with the solution containing hydrogenation active metals salt and is dried, is calcined and reduces successively, obtain supported catalyst；Wherein, the molecular sieve is the molecular sieve with one-dimensional oval pore structure, and the short axle of the one-dimensional oval pore structure isThe major axis of the one-dimensional oval pore structure is
Description
Technical field
This disclosure relates to a kind of preparation method of catalyst for hydrogenation de-waxing and the catalyst prepared by this method and the catalysis
The application of agent.
Background technology
Being produced by waxy feeds has the product of good flow performance under low temperature, such as lubricating oil, jet fuel, low-coagulation diesel oil
Deng dewaxing is necessary.Wherein described wax refers to long-chain normal paraffin or the long-chain hydrocarbon compound with a small amount of short-side chain,
Including the long chain alkane with a small amount of short-side chain, chain alkyl aromatic hydrocarbons and chain alkyl cycloalkane.Traditional process for dewaxing uses
Solvent dewaxing process, the major defect of the technique is that running cost is very high, and energy consumption is big, and condensation point reduces limited extent.It is another
Process for dewaxing is catalytic dewaxing, and this method is unique duct and appropriate acid using molecular sieve catalyst under hydro condition
Property, at certain temperature and hydrogen dividing potential drop, crack with making the wax compositional selecting in feedstock oil, so as to reduce its condensation point.It is this
The shortcomings that method is gas yield height, and the yield of base oil is low, and viscosity index (VI) loss is big.More satisfactory process for dewaxing is at present
Hydroisomerizing dewaxes, and using the molecular sieve catalyst with unique pore passage structure, only allows macromolecular wax to enter molecular sieve pore passage
Middle generation isomerization reaction generation isoparaffin, and other isoparaffins, cycloalkane and aromatic hydrocarbons etc. then cannot be introduced into, and thus reach
The effect of selectively removing wax component.Because isoparaffin has relatively low condensation point and higher viscosity index (VI), therefore in pour point depression
While, the viscosity index (VI) of base oil is higher, and yield is also apparently higher than catalytic dewaxing process.
There are a large amount of patent reports about isomerization dewaxing catalyst and technique, such as U.S. Patent application both at home and abroad at present：US
20050000857th, US 20040134834 and US 20040065585 etc., United States Patent (USP)：USP6602402、USP6264826、
USP6235960、USP6231749、USP6198015、USP6190532、USP6090989、USP6051129、USP5993644、
USP5990371、USP5976351、USP5885438、USP5358628、USP5149421、USP5135638、USP5037528
With USP4419420 etc., Chinese patent application：CN102051220A, CN1703497A, CN1703493A, CN1703292A and
CN1703275A etc., wherein isomerization dewaxing catalyst acidic components include Beta, ZSM-5, ZSM-11, ZSM-12, ZSM-22,
ZSM-23, ZSM-35, ZSM-48, ZSM-57, modenite, SAPO-11, SAPO-31, SAPO-41, NU-10, NU-13, NU-
87th, EU-1, EU-2, EU-11, EU-13, Theta-1, ITQ-13, SSZ-32 and ferrierite etc..
Because lube cut is mainly macromolecule hydrocarbon, molecular structure is complicated, and these hydro carbons are in isomerization dewaxing catalyst
It is upper to occur different reaction, include the cracking etc. of the saturation of aromatic hydrocarbons, isomerization of paraffins and alkane.During Hydrodewaxing,
In order to ensure higher base oil yield, it is necessary to reduce the side reactions such as the cracking of alkane as far as possible, the isomery selection of catalyst is improved
Property.
The content of the invention
The catalyst that the purpose of the disclosure is to provide a kind of preparation method of catalyst for hydrogenation de-waxing and prepared by this method
And the application of the catalyst, during Hydrodewaxing is applied to using the catalyst prepared by disclosed method, not only urge
The selectivity of agent improves, and can more effectively reduce the pour point of heavy lubricant base stock, and keeps higher purpose production
Product yield.
To achieve these goals, the disclosure provides a kind of preparation method of catalyst for hydrogenation de-waxing, the preparation method bag
Include：A, molecular sieve-inorganic oxide carrier is subjected to the first dipping with the solution containing hydrogenation active metals salt and carried out successively
Dry, be calcined and reduce, obtain supported catalyst；Wherein, the molecular sieve is the molecular sieve with one-dimensional oval pore structure, institute
The short axle for stating one-dimensional oval pore structure is The major axis of the one-dimensional oval pore structure isB, by step
The supported catalyst of gained carries out the second dipping with the aqueous solution containing organic compound and dried in a, obtains Hydrodewaxing catalysis
Agent；Wherein, the organic compound includes organic amine and alcohol, and/or including organic alcohol amine.
Preferably, organic amine described in step b is at least one of triethylamine, tripropyl amine (TPA) and tri-n-butylamine, the alcohol
For selected from least one of methanol, ethanol, propyl alcohol, butanol and ethylene glycol, the organic alcohol amine is diethanol amine and/or three second
Hydramine.
Preferably, the amount of the material of the nitrogen described in step b in the aqueous solution containing organic compound with butt matter
The ratio of the supported catalyst of gauge is 50-200 micromoles per grams；Nitrogen in the aqueous solution containing organic compound
Substance withdrawl syndrome be 50-200 mM/ls, the substance withdrawl syndrome of hydroxyl is 50-400 mM/ls, wherein, it is described
Hydroxyl comes from alcohol and/or hydramine.
Preferably, in terms of butt, the content of molecular sieve is 20-80 mass % in the molecular sieve-inorganic oxide carrier.
Preferably, the molecular sieve is selected from ZSM-22, ZSM-23, ZSM-35, ZSM-48, NU-10, Theta-1, EU-
At least one of 13 and ferrierite.
Preferably, the inorganic oxide is selected from least one of aluminum oxide, silica and silica-alumina.
Preferably, the preparation process of the molecular sieve-inorganic oxide carrier includes：Molecular sieve and inorganic oxide will be contained
The mixture of thing presoma is molded and is calcined successively.
Preferably, the roasting condition described in the preparation process of the molecular sieve-inorganic oxide carrier is：Sintering temperature
For 400-650 DEG C, roasting time is 1-15 hours.
Preferably, hydrogenation active metals salt described in step a contains at least one in cobalt, nickel, ruthenium, rhodium, palladium and platinum
Kind hydrogenation active metals element；On the basis of the gross mass of catalyst for hydrogenation de-waxing, add described in the catalyst for hydrogenation de-waxing
The content of hydrogen activity metallic element is 0.1-5 mass %.
Preferably, hydrogenation active metals salt contains platinum and palladium described in step a.
Preferably, condition dry described in step a is：Temperature is 100-200 DEG C, and the time is 2-12 hours；In step a
The condition of the roasting is：Temperature is 300-550 DEG C, and the time is 1-15 hours.
Preferably, the condition reduced described in step a is：The temperature of the reduction is 300-550 DEG C, and the time of reduction is
2-10 hours, Hydrogen Vapor Pressure are 0.01-2.0 MPas.
Preferably, condition dry described in step b is：Temperature is 100-150 DEG C, and the time is 0.5-4 hours.
The Hydrodewaxing that the disclosure also provides prepared by the preparation method for the catalyst for hydrogenation de-waxing that the disclosure is provided is urged
Agent.
The disclosure also provides the application of catalyst for hydrogenation de-waxing that the disclosure provided in Hydrodewaxing reaction, the application
Including：Hydrodewaxing raw material feeding hydrodewaxing unit is contacted with the catalyst for hydrogenation de-waxing and that Hydrodewaxing occurs is anti-
Should.
Preferably, the Hydrodewaxing raw material is under hydrocracking tail oil, hydrogenation distillate, frivolous coal tar, wax
At least one of oil, soft wax, Fischer Tropsch waxes and biology boat coal.
Preferably, the condition of the Hydrodewaxing reaction is：Reaction temperature is 300-420 DEG C, and hydrogen dividing potential drop is 0.5-15 million
Pa, liquid volume air speed are 0.1-5 hours-1, hydrogen to oil volume ratio 100-3000.
Compared with prior art, it is applied to the Hydrodewaxing of waxy distillate using the catalyst prepared by disclosed method
Process, including but not limited to hydrocracking tail oil, hydrogenation distillate, frivolous coal tar, sweat oil, soft wax, Fischer Tropsch waxes, life
Thing boat coal etc., its stereoselectivity is high, and when being reduced to same pour point, base oil yield is high.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the disclosure is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explained the disclosure, is not limited to the disclosure.
The disclosure provides a kind of preparation method of catalyst for hydrogenation de-waxing, and the preparation method includes：A, by molecular sieve-inorganic
Oxide carrier carries out the first dipping with the solution containing hydrogenation active metals salt and is dried, is calcined and reduces successively, obtains
To supported catalyst；Wherein, the molecular sieve is the molecular sieve with one-dimensional oval pore structure, the one-dimensional oval pore structure
Short axle isThe major axis of the one-dimensional oval pore structure isB, by the supported catalyst of gained in step a
Agent carries out the second dipping with the aqueous solution containing organic compound and dried, and obtains catalyst for hydrogenation de-waxing；Wherein, it is described to organise
Compound includes organic amine and alcohol, and/or including organic alcohol amine.
The inventor of the disclosure by impregnating the aqueous solution containing organic compound it was unexpectedly observed that make catalyst for hydrogenation de-waxing
Amount of activated center acid strength change, can adjust catalyst activity and improve catalyst stereoselectivity, step b
Described in organic amine, alcohol and hydramine be well-known to those skilled in the art, for example, organic amine described in step b be triethylamine,
At least one of tripropyl amine (TPA) and tri-n-butylamine, the alcohol be in methanol, ethanol, propyl alcohol, butanol and ethylene glycol at least
One kind, the organic alcohol amine are diethanol amine and/or triethanolamine.
According to the disclosure, the amount disclosure of organic compound used in dipping is not particularly limited, that can adjust
The acidity of catalyst is defined, for example, the amount of the material of the nitrogen described in step b in the aqueous solution containing organic compound with
The ratio of the supported catalyst of butt quality meter is 50-200 micromoles per grams, preferably 80-150 micromoles per grams；It is described
The substance withdrawl syndrome of nitrogen is 50-200 mM/ls, preferably 80-150 mmoles in the aqueous solution containing organic compound
You/liter, the substance withdrawl syndrome of hydroxyl is 50-400 mM/ls, preferably 200-300 mM/ls, wherein, the hydroxyl
Base comes from alcohol and/or hydramine.
Known in those skilled in the art to be according to the disclosure, catalyst for hydrogenation de-waxing needs the molecule of one-dimensional channels
Sieve, so that the wax molecular moiety of long-chain or the duct completely into molecular sieve, so as to which isomerization reaction occur, wherein, institute in step a
The molecular sieve stated can be selected from ZSM-22, ZSM-23, ZSM-35, ZSM-48, NU-10, Theta-1, EU-13 and ferrierite
At least one of, the preparation method of above-mentioned molecular sieve is disclosed in various documents, such as United States Patent (USP) USP 4481177, USP
5332566th, USP 4900528, USP 5053373 etc., here as quotation is referred to；Described inorganic oxide can be
Selected from least one of aluminum oxide, silica and silica-alumina, preferably aluminum oxide；In terms of butt, the molecule
The content of molecular sieve can be 20-80 mass % in sieve-inorganic oxide carrier.
According to the disclosure, the preparation process of the molecular sieve-inorganic oxide carrier can include：Will contain molecular sieve and
The mixture of inorganic oxide precursor body is molded and is calcined successively, and the condition of the roasting can be：Sintering temperature is
400-650 DEG C, roasting time is 1-15 hours.Wherein described inorganic oxide precursor body refers to that by roasting nothing can be turned into
The compound of machine oxide, such as boehmite, boehmite, silica gel, amorphous silica-alumina and other people in the art
The compound that member commonly uses.
According to a kind of embodiment of the disclosure, the preparation method of the molecular sieve-inorganic oxide carrier can be with
For：The molecular sieve is mixed with the matrix, extruded moulding, be then dried and be calcined.In the side using extrusion molding
Method can add appropriate extrusion aid and/or adhesive, then extrusion molding when being molded.The extrusion aid, peptizing agent species and
Dosage is known to those skilled in the art, will not be described here.The temperature of the drying is preferably 100-200 DEG C, further excellent
Elect 120-150 DEG C as, drying time is preferably 1-20 hours, more preferably 2-10 hours.The temperature of the roasting is preferred
For 400-650 DEG C, more preferably 500-600 DEG C, roasting time is preferably 1-15 hours, and more preferably 2-10 is small
When.
According to the disclosure, the hydrogenation active metals salt can contain hydrogenation activity gold using solubility commonly used in the art
The salt of category, such as can be one kind or several in nitrate, acetate, carbonate, chloride and soluble complexes
Kind；Hydrogenation active metals can be loaded in the impregnated carrier by the dipping method such as soaking or spraying, and can be carried out afterwards
Dry, roasting and reduction step；Dry condition can be described in step a：Temperature is 100-200 DEG C, preferably 120-150
DEG C, the time is 2-12 hours, preferably 2-10 hours；The condition of roasting described in step a can be：Temperature is 300-550
DEG C, preferably 350-500 DEG C, the time is 1-15 hours, preferably 2-10 hours；The condition reduced described in step a can be：
The temperature of the reduction is 300-550 DEG C, and the time of reduction is 2-10 hours, reduces and is carried out in hydrogen atmosphere, Hydrogen Vapor Pressure
For 0.01-2.0 MPas.Wherein, hydrogenation active metals salt described in step a can contain one kind in group VIII metal or several
Kind, it is selected from least one of cobalt, nickel, ruthenium, rhodium, palladium and platinum hydrogenation active metals element；Catalyst for hydrogenation de-waxing it is total
On the basis of quality, the content of hydrogenation active metals element described in the catalyst for hydrogenation de-waxing can be 0.1-5 mass %, excellent
Elect 0.2-2 mass % as.Disclosed method is preferably, and hydrogenation active metals salt described in step a can contain platinum and palladium.
When described hydrogenation active metal component is platinum and palladium, the hydrogenation active metals salt can include PtCl4、Pt(NO3)2、
H2PtCl6、Pt(NH3)4Cl2、Pt(NH3)2(NO2)2With Pt (NH3)4(NO3)2And PdCl2、Pd(NO3)2、H2PdCl4、Pd
(NH3)4Cl2With Pd (NH3)4(NO3)2Deng.
According to the disclosure, the condition dried described in step b can be：Temperature is 100-150 DEG C, and the time is that 0.5-4 is small
When.
The hydrogenation that the disclosure also provides prepared by the preparation method of the catalyst for hydrogenation de-waxing provided according to the disclosure takes off
Wax catalyst.
The disclosure also provides a kind of application of catalyst for hydrogenation de-waxing that disclosure provided in Hydrodewaxing reaction, should
Using including：Hydrodewaxing raw material feeding hydrodewaxing unit is contacted with the catalyst for hydrogenation de-waxing and Hydrodewaxing occurs
Reaction.
According to the disclosure, the Hydrodewaxing raw material can use the conventional raw material in this area, if boiling point is more than 170 DEG C
Waxy feeds oil, such as can be selected from hydrocracking tail oil, hydrogenation distillate, frivolous coal tar, sweat oil, soft wax, Fischer-Tropsch
At least one of synthetic wax (heavy waxy feeds) and biology boat coal.The condition of the Hydrodewaxing reaction can also be ability
The conventional reaction condition in domain, for example, reaction temperature can be 300-420 DEG C, hydrogen dividing potential drop can be 0.5-15 MPas, liquid volume
Air speed can be 0.1-5 hours-1, hydrogen to oil volume ratio can be 100-3000.
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
Instrument is the conventional use of instrument of those skilled in the art institute unless otherwise specified used by the embodiment of the present disclosure；Made
Reagent, it is chemically pure reagent unless otherwise instructed.
The embodiment of the present disclosure determines the content of hydrogenation active metals in catalyst using RIPP 132-90 test methods.
C5 +Liquid is received to be calculated using equation below：C5 +Liquid receipts=C5 +Products weight/total product weight.
>370 DEG C of yields are calculated using equation below：>370 DEG C of yields=>370 DEG C of products weight/total product weights.
Pour point is measured using GB/T3535-2006 national standard method.
40 DEG C of viscosity and viscosity index (VI) are measured using GB/T 1995-1998 national standard method.
RIPP test methods described in the disclosure are selected from《Petrochemical Engineering Analysis method (RIPP test methods)》, Yang Cui is fixed etc.
Compile, Science Press, 1990.
Embodiment 1
Illustrate catalyst that the disclosure provides and preparation method thereof.
Crystallization 96 is carried out after organic formwork agent, silicon source and silicon source are mixed in 400Rpm, 160 DEG C of stainless steel cauldron
Hour, obtain 100%ZSM-22 molecular sieves.Wherein, organic formwork agent is ethyl pyridinium bromide, and silicon source is Al2(SO4)3·
16H2O, silicon source are Ludox (SiO2Content is 30 heavy %), the SiO to feed intake2/Al2O3For 60, H2O/SiO2For 40, OH-/SiO2
For 0.3, K+/SiO2For 0.43, template/SiO2Silica alumina ratio for 0.2, ZSM-22 molecular sieves is 67.By gained molecular sieve
100 grams with containing 20 weight %NH4NO31000 milliliters of solution handled 4 hours at 80 DEG C, filter, method described above coprocessing 3
It is secondary.Molecular sieve after processing is dried 4 hours at 120 DEG C.Obtain Hydrogen ZSM-22 molecular sieves.
Hydrogen ZSM-22 molecular sieves are well mixed with a certain amount of boehmite, sesbania powder, add aqueous solution of nitric acid,
Abundant kneading, a diameter of 1.3 millimeters of cloverleaf pattern bar is then extruded on banded extruder, it is dry 4 hours at 120 DEG C, then
570 DEG C are calcined 4 hours in atmosphere, obtain carrier S 1.
100 grams of carrier Ss 1 are used and contain 702 milligrams of Pt (NH3)4Cl2Solution carry out saturation dipping, then at 120 DEG C do
Dry 4 hours, 350 DEG C were calcined 4 hours in air atmosphere.Then gained catalyst being reduced, reduction temperature is 350 DEG C,
Recovery time is 4 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Catalyst after reduction is with 100 milliliters of tri-n-butylamines and ethanol water
The mol ratio of dipping 1 hour, wherein 100 mM/ls of the concentration of tri-n-butylamine, ethanol and tri-n-butylamine is 2:1.Filtering, so
120 DEG C of dryings 4 hours afterwards, gained catalyst is designated as C1, and its composition is shown in Table 1.
Embodiment 2
Illustrate catalyst that the disclosure provides and preparation method thereof.
By Ludox (SiO2Content is 30 heavy %), Al2(SO4)3·18H2O, KOH, sulfuric acid, organic directing agent, deionization
Water is mixed to form gel, is put into 300ml Teflon stainless steel stirred autoclave and crystallization is carried out at 170 DEG C 96 hours, brilliant
After change terminates, purified product obtains ZSM-23 molecular screen through cooling down, washing and dry.Wherein, the SiO to feed intake2/Al2O3For 90,
H2O/SiO2For 60, OH-/SiO2For 0.25, K+/SiO2For 0.27, template/SiO2For 0.08, crystallization time is 96 hours, brilliant
It is 170 DEG C to change temperature, and the silica alumina ratio of ZSM-23 molecular screen is 82.Gained molecular sieve is prepared according to the method for embodiment 1
Into hydrogen type molecular sieve.
Hydrogen ZSM-23 molecular screen is well mixed with a certain amount of boehmite, sesbania powder, adds aqueous solution of nitric acid,
Abundant kneading, a diameter of 1.3 millimeters of cloverleaf pattern bar is then extruded on banded extruder, it is dry 2 hours at 150 DEG C, then
600 DEG C are calcined 3 hours in atmosphere, obtain carrier S 2.
100 grams of carrier Ss 2 are used and contain 399 milligrams of Pd (NH3)2Cl2With 878 milligrams of Pt (NH3)4Cl2Solution carry out saturation
Dipping, then dried 4 hours at 120 DEG C, 400 DEG C are calcined 3 hours in air atmosphere.Then gained catalyst is gone back
Original, reduction temperature are 350 DEG C, and the recovery time is 3 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Catalyst after reduction is with 80 milliliter two
Aqueous ethanolamine impregnates 3 hours, and the concentration of the diethanol amine aqueous solution is 80 mM/ls.Filtering, then 120 DEG C of dryings 4 are small
When, gained catalyst is designated as C2, and its composition is shown in Table 1.
Embodiment 3
Illustrate catalyst that the disclosure provides and preparation method thereof.
The gained Hydrogen ZSM-22 molecular sieves of embodiment 1 are well mixed with a certain amount of boehmite, sesbania powder, added
Aqueous solution of nitric acid, abundant kneading, a diameter of 1.3 millimeters of cloverleaf pattern bar is then extruded on banded extruder, dried at 120 DEG C
4 hours, then in atmosphere 550 DEG C be calcined 4 hours, obtain carrier S 3.
100 grams of carrier Ss 3 are used and contain 820 milligrams of RuCl3With 1067 milligrams of Pd (NH3)4(NO3)2Solution carry out saturation leaching
Stain, then dried 6 hours at 120 DEG C, 400 DEG C are calcined 3 hours in air atmosphere.Then gained catalyst is gone back
Original, reduction temperature are 300 DEG C, and the recovery time is 3 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Catalyst after reduction is with 100 milliliters
Triethylamine and aqueous propanol solution impregnate 2 hours, and the concentration of triethylamine is 150 mM/ls, and the mol ratio of propyl alcohol and triethylamine is
2:1.Filtering, then 120 DEG C of dryings 2 hours, gained catalyst is designated as C3, and its composition is shown in Table 1.
Comparative example 1
Illustrate comparative catalyst and preparation method thereof.
100 grams of carrier Ss 1 are used and contain 702 milligrams of Pt (NH3)4Cl2Solution carry out saturation dipping, then at 120 DEG C do
Dry 4 hours, 350 DEG C were calcined 4 hours in air atmosphere.Then gained catalyst being reduced, reduction temperature is 350 DEG C,
Recovery time is 4 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Catalyst after reduction is designated as D1, and its composition is shown in Table 1.
Comparative example 2
Illustrate comparative catalyst and preparation method thereof.
100 grams of carrier Ss 2 are used and contain 399 milligrams of Pd (NH3)2Cl2With 878 milligrams of Pt (NH3)4Cl2Solution carry out saturation
Dipping, then dried 4 hours at 120 DEG C, 400 DEG C are calcined 3 hours in air atmosphere.Then gained catalyst is gone back
Original, reduction temperature are 350 DEG C, and the recovery time is 3 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Catalyst after reduction is designated as D2, its
Composition is shown in Table 1.
Comparative example 3
100 grams of carrier Ss 3 are used and contain 820 milligrams of RuCl3With 1067 milligrams of Pd (NH3)4(NO3)2Solution carry out saturation leaching
Stain, then dried 6 hours at 120 DEG C, 400 DEG C are calcined 3 hours in air atmosphere.Then gained catalyst is gone back
Original, reduction temperature are 300 DEG C, and the recovery time is 3 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Gained catalyst is designated as D3, and it is formed
It is shown in Table 1.
Embodiment 4-6
This example demonstrates that the performance for the catalyst that the disclosure provides.
Evaluating catalyst, its property are carried out using a kind of hydrocracking tail oil (coming from Sinopec Maoming Petrochemical branch company)
It is shown in Table 2.Reaction is carried out on 100 milliliters of hydrogenation reaction devices, and catalyst particle diameter is 0.30~0.45 millimeter.Process conditions
3 are shown in Table with reaction result.
Comparative example 4
It is essentially identical with the condition of embodiment 4, except that catalyst is D1.Process conditions and reaction result are shown in Table 3.
Comparative example 5
It is essentially identical with the condition of embodiment 5, except that catalyst is D2.Process conditions and reaction result are shown in Table 3.
Comparative example 6
It is essentially identical with the condition of embodiment 6, except that catalyst is D3.Process conditions and reaction result are shown in Table 3.
Comparative example 7
It is identical with the condition of embodiment 4, except that using catalyst D1, and initial reaction stage, catalyst is with containing three positive fourths
The feedstock oil of amine and ethanol is handled, and wherein the mol ratio of ethanol and tri-n-butylamine is 2:1, control the oil-feed time so that place
The ratio of nitrogen and catalyst is 100 micromoles per gram catalyst during reason.Normal feedstock oil is then switched to, is warming up to required
Reaction temperature is tested.Process conditions and reaction result are shown in Table 3.
The result of table 3 shows that the catalyst of the disclosure is applied to have more preferably during the Hydrodewaxing process of waxy feeds oil
Activity and stereoselectivity, compared with comparative catalyst, generation oil pour point it is suitable when, using the disclosure provide catalysis
Agent generates the lube base oil yield of oil (in table 3 obtained by being reacted>370 DEG C of yields) it is higher, liquid receive also apparently higher than
Comparative catalyst.
Table 1
Table 2
| Density (20 DEG C), gcm-3 | 0.8372 |
| Pour point, DEG C | +36 |
| Sulfur content, μ gg-1 | 2.5 |
| Nitrogen content, μ gg-1 | 2.6 |
| Viscosity (forward flow process) | |
| 40 DEG C of viscosity, mm2/s | 16.46 |
| 100 DEG C of viscosity, mm2/s | 3.812 |
| Viscosity index (VI) | 124 |
Table 3
Claims (17)
1. a kind of preparation method of catalyst for hydrogenation de-waxing, the preparation method include：
A, molecular sieve-inorganic oxide carrier is subjected to the first dipping with the solution containing hydrogenation active metals salt and carried out successively
Dry, be calcined and reduce, obtain supported catalyst；Wherein, the molecular sieve is the molecular sieve with one-dimensional oval pore structure, institute
The short axle for stating one-dimensional oval pore structure isThe major axis of the one-dimensional oval pore structure is
B, the supported catalyst of gained in step a is subjected to the second dipping with the aqueous solution containing organic compound and dried, obtained
Catalyst for hydrogenation de-waxing；Wherein, the organic compound includes organic amine and alcohol, and/or including organic alcohol amine.
2. preparation method according to claim 1, wherein, organic amine described in step b be triethylamine, tripropyl amine (TPA) and three just
At least one of butylamine, the alcohol be selected from least one of methanol, ethanol, propyl alcohol, butanol and ethylene glycol, it is described organic
Hydramine is diethanol amine and/or triethanolamine.
3. preparation method according to claim 1, wherein, the nitrogen described in step b in the aqueous solution containing organic compound
The amount of the material of element and the ratio for the supported catalyst counted using butt quality is 50-200 micromoles per grams；It is described containing
The substance withdrawl syndrome of nitrogen is 50-200 mM/ls in the aqueous solution of machine compound, and the substance withdrawl syndrome of hydroxyl is
50-400 mM/ls, wherein, the hydroxyl comes from alcohol and/or hydramine.
4. preparation method according to claim 1, wherein, in terms of butt, divide in the molecular sieve-inorganic oxide carrier
The content of son sieve is 20-80 mass %.
5. preparation method according to claim 1, wherein, the molecular sieve be selected from ZSM-22, ZSM-23, ZSM-35,
At least one of ZSM-48, NU-10, Theta-1, EU-13 and ferrierite.
6. preparation method according to claim 1, wherein, the inorganic oxide is selected from aluminum oxide, silica and oxygen
At least one of SiClx-aluminum oxide.
7. preparation method according to claim 1, wherein, the preparation process bag of the molecular sieve-inorganic oxide carrier
Include：Mixture containing molecular sieve and inorganic oxide precursor body is molded and is calcined successively.
8. preparation method according to claim 7, wherein, in the preparation process of the molecular sieve-inorganic oxide carrier
Described roasting condition is：Sintering temperature is 400-650 DEG C, and roasting time is 1-15 hours.
9. preparation method according to claim 1, wherein, hydrogenation active metals salt described in step a contain selected from cobalt,
At least one of nickel, ruthenium, rhodium, palladium and platinum hydrogenation active metals element；On the basis of the gross mass of catalyst for hydrogenation de-waxing, institute
The content for stating hydrogenation active metals element described in catalyst for hydrogenation de-waxing is 0.1-5 mass %.
10. preparation method according to claim 9, wherein, hydrogenation active metals salt contains platinum and palladium described in step a.
11. preparation method according to claim 1, wherein, the condition dried described in step a is：Temperature is 100-200
DEG C, the time is 2-12 hours；The condition being calcined described in step a is：Temperature is 300-550 DEG C, and the time is 1-15 hours.
12. preparation method according to claim 1, wherein, the condition reduced described in step a is：The temperature of the reduction
Spend for 300-550 DEG C, the time of reduction is 2-10 hours, and Hydrogen Vapor Pressure is 0.01-2.0 MPas.
13. preparation method according to claim 1, wherein, the condition dried described in step b is：Temperature is 100-150
DEG C, the time is 0.5-4 hours.
14. the hydrogenation according to prepared by the preparation method of the catalyst for hydrogenation de-waxing described in claim 1-13 any one takes off
Wax catalyst.
15. application of the catalyst for hydrogenation de-waxing in Hydrodewaxing reaction described in claim 14, the application include：Will hydrogenation
Dewaxed feedstock is sent into hydrodewaxing unit and is contacted with the catalyst for hydrogenation de-waxing and Hydrodewaxing reaction occurs.
16. application according to claim 15, wherein, the Hydrodewaxing raw material is selected from hydrocracking tail oil, hydrogenation cut
At least one of oily, frivolous coal tar, sweat oil, soft wax, Fischer Tropsch waxes and biology boat coal.
17. application according to claim 15, wherein, the condition of the Hydrodewaxing reaction is：Reaction temperature is 300-420
DEG C, hydrogen dividing potential drop is 0.5-15 MPas, and liquid volume air speed is 0.1-5 hours-1, hydrogen to oil volume ratio 100-3000.
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