CN104971698B - One kind contains R1R2R3R4N+X‑Aluminum oxide article shaped and its preparation and application - Google Patents
One kind contains R1R2R3R4N+X‑Aluminum oxide article shaped and its preparation and application Download PDFInfo
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Abstract
One kind contains R1R2R3R4N+X‑Aluminum oxide article shaped and its preparation and application, contain R1R2R3R4N+X‑, wherein, the R1R2R3R4N+X‑Mass fraction be 0.1% 10%, the R1R2R3R4N+X‑One or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein the R1、R2、R3、R4Selected from hydrogen, hydrocarbon substituent and its derivative.The article shaped can be applied to adsorbent and catalyst carrier.
Description
Technical field
The present invention relates to aluminum oxide and its preparation and application, contain R more specifically to one kind1R2R3R4N+X-Oxidation
Aluminium article shaped and its preparation and application.
Background technology
Aluminum oxide with porous property（Include the aluminum oxide of the porous property containing addO-on therapy）, because it is with higher
Specific surface area and pore volume, be often used as adsorbent and matrix use as catalyst carrier.For example, in PETROLEUM PROCESSING field,
The carrier that aluminum oxide is often used as being hydrogenated with class catalyst uses.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind to contain R1R2R3R4N+X-Aluminum oxide article shaped, the article shaped
Preparation method and applications.
The present invention relates to herein below：
1. one kind contains R1R2R3R4N+X-Aluminum oxide article shaped, contain R1R2R3R4N+X-, on the basis of the article shaped,
The R1R2R3R4N+X-Mass fraction be 0.1%-10%, the R1R2R3R4N+X-Selected from primary amine salt, secondary amine salt, tertiary ammonium salt or
One or more in quaternary ammonium salt, wherein the R1、R2、R3、R4Derivative or hydrogen selected from hydrocarbon substituent, hydrocarbon substituent.
2. the article shaped according to 1, it is characterised in that on the basis of the article shaped, the R1R2R3R4N+X-Matter
Amount fraction is 0.3%-5%.
3. the article shaped according to 1, it is characterised in that the hydrocarbon substituent is selected from C1-C20 straight or branched alkane
Base, or the cycloalkyl selected from C3-C20, or the aryl selected from C6-C20；The derivative of the hydrocarbon substituent is selected from band
There is the alkyl of hydroxyl and/or heterocyclic substituent.
4. the article shaped according to 3, it is characterised in that the hydrocarbon substituent is selected from C1-C18 straight or branched alkane
Base；The either cycloalkyl selected from C6-C18；The either aryl selected from C6-C18.
5. according to the article shaped described in 1,2 or 3 any one, it is characterised in that the X is selected from chlorine, bromine or iodine.
6. the article shaped according to 5, it is characterised in that the X is selected from chlorine or bromine.
7. according to the article shaped described in 1,2 or 3 any one, it is characterised in that the R1R2R3R4N+X-Selected from cetyl
Trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, myristyl
Trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC,
Didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyls two
Ammonio methacrylate, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double octadecyldimethyl brominations
Ammonium, dioctadecyl dimethyl ammonium chloride, DTAB and DTAC one kind or
It is a variety of.
8. according to the article shaped described in 1,2 or 3 any one, it is characterised in that the R1R2R3R4N+X-Selected from ethanolamine salt,
Dococylpyridinium hydrochloride.
9. the article shaped according to 1, it is characterised in that contain in the article shaped selected from silica, titanium oxide, oxidation
One or more of adjuvant components in magnesium, zirconium oxide, thorium oxide, beryllium oxide, on the basis of the article shaped, the adjuvant component
Mass fraction be less than 10%.
10. the article shaped according to 9, it is characterised in that on the basis of the article shaped, the quality of the adjuvant component
Fraction is 0.3%-5%.
11. according to the article shaped described in 1 or 9, it is characterised in that contain clay and/or molecular sieve in the article shaped, with
On the basis of the article shaped, the mass fraction of the clay and/or molecular sieve is less than 35%.
12. the article shaped according to 11, it is characterised in that on the basis of the article shaped, the clay and/or molecule
The mass fraction of sieve is 1%-20%.
13. one kind contains R1R2R3R4N+X-Aluminum oxide article shaped preparation method, be included in the aluminum oxide article shaped
Middle introducing R1R2R3R4N+X-, on the basis of the article shaped, the R1R2R3R4N+X-Introduction volume make in the article shaped
R1R2R3R4N+X-Mass fraction is 0.1%-10%, the R1R2R3R4N+X-Selected from primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt
In one or more, wherein the R1、R2、R3、R4Derivative or hydrogen selected from hydrocarbon substituent, hydrocarbon substituent.
14. the method according to 13, it is characterised in that on the basis of the article shaped, the R1R2R3R4N+X-Draw
Entering amount makes R in the article shaped1R2R3R4N+X-Mass fraction be 0.3%- 5%.
15. the method according to 13, it is characterised in that the hydrocarbon substituent is selected from C1-C20 straight or branched alkane
Base, or the cycloalkyl selected from C3-C20, or the aryl selected from C6-C20；The substitution of the derivative of the hydrocarbon substituent
Base is selected from the alkyl with hydroxyl and/or heterocyclic substituent.
16. the method according to 15, it is characterised in that the substituent of the hydrocarbon is selected from C1-C18 straight or branched alkane
Base；The either cycloalkyl selected from C6-C18；The either aryl selected from C6-C18.
17. according to the method described in 13,14 or 15 any one, it is characterised in that the X is selected from chlorine, bromine or iodine.
18. according to the method described in 13,14 or 15 any one, it is characterised in that the R1R2R3R4N+X-Selected from hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, the tetradecane
Base trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorination
Ammonium, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecanes
Base alkyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double octadecyldimethyls
Ammonium bromide, dioctadecyl dimethyl ammonium chloride, the one of DTAB and DTAC
Kind is a variety of.
19. according to the method described in 13,14 or 15 any one, it is characterised in that the R1R2R3R4N+X-Selected from monoethanolamine
Salt, dococylpyridinium hydrochloride.
20. the method according to 13, it is characterised in that be included in introducing in the article shaped in the process and be selected from
The step of one or more of adjuvant components in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, with described
On the basis of article shaped, the introduction volume of the adjuvant component makes the mass fraction of adjuvant component in the article shaped be less than 10%.
21. the method according to 20, it is characterised in that on the basis of the article shaped, the quality of the adjuvant component
Fraction is 0.3%-5%.
22. according to the method described in 13 or 20, it is characterised in that contain clay and/or molecular sieve in the article shaped, with
On the basis of the article shaped, the mass fraction of the clay and/or molecular sieve is less than 35%.
23. the method according to 22, it is characterised in that on the basis of the article shaped, the clay and/or molecule
The mass fraction of sieve is 1%-20%.
24. the method according to 13, it is characterised in that described to introduce R in the aluminum oxide article shaped1R2R3R4N+
X-Method, including：（1）With containing R1R2R3R4N+X-Solution impregnate the aluminum oxide article shaped, the volume of the maceration extract with
The ratio between pore volume of the article shaped is 0.5-20；（2）The mixture that dipping obtains is heat-treated in closed reactor,
Heat treatment temperature be room temperature to 250 DEG C, the time is -48 hours 0.5 hour；（3）Drying steps（2）Product, the dried strip
Part includes：Temperature is 40 DEG C -250 DEG C, and the time is -24 hours 1 hour.
25. the method according to 24, it is characterised in that step（1）Described in maceration extract volume and the article shaped
The ratio between pore volume be 1-15；Step（2）Described in heat treatment temperature be 60 DEG C to 220 DEG C, the time be -36 hours 1 hour,
Step（3）Drying condition include：Temperature is 100 DEG C -180 DEG C, and the time is -18 hours 2 hours.
26. according to application of any one of 1-12 article shapeds as adsorbent.
27. according to application of any one of 1-12 article shapeds as catalyst carrier.
In the present invention, the aluminum oxide can be the one or more in γ, η, θ, δ and χ, preferably gamma oxidation
Aluminium.The aluminum oxide has ratio surface and the pore volume of conventional alumina, and the ratio surface of preferential oxidation aluminium is 150-350 rice2/
Gram, more preferably 180-320 rice2/ gram, preferably the pore volume of aluminum oxide is 0.4-1.1 mls/g, more preferably
0.5-0.9 mls/g.They can be that commercially available commodity can also be prepared by any one method in the prior art.For example, can be with
It is by one or more of after being molded, being calcined in hibbsite, monohydrate alumina and amorphous hydroted alumina
It is made.
The shaping of the aluminum oxide is carried out using customary way, such as the methods of tabletting, spin, extrusion.Using
When customary way is molded, to ensure that what is be molded is smoothed out to foregoing material to be formed（For example, hibbsite, one
One or more of mixtures in hydrated alumina and amorphous hydroted alumina）Middle introducing auxiliary agent is allowed, such as when crowded
During bar, appropriate extrusion aid and water, afterwards extrusion molding can be introduced into foregoing material to be formed.The species of the extrusion aid
And to may each be this area conventional for dosage, such as common extrusion aid can be selected from sesbania powder, methylcellulose, starch, poly-
One or more in vinyl alcohol, PVOH.
In one preferred embodiment, boehmite and/or vacation of the aluminum oxide article shaped for a kind of modification
The gama-alumina that boehmite obtains after being molded, being calcined.
The method of the modified boehmite and/or false boehmite includes：（1）By at least one alumina hydration
Thing is calcined, and the roasting condition includes：Temperature is 300 DEG C -950 DEG C, and the time is -24 hours 0.5 hour；（2）By step（1）
The product of roasting arrived mixes with least one boehmite and/or false boehmite and water, obtains a kind of mixture；
（3）By step（2）Obtained mixture carries out hydro-thermal process in closed reactor, and hydrothermal conditions include：Temperature is 60
DEG C -250 DEG C, the time is -48 hours 0.5 hour；（4）By step（3）Obtained product is dried, and obtains modified boehmite
And/or false boehmite.
Wherein, the preferable step（1）Roasting condition include：Temperature is 300-750 DEG C, and the time is 1-24 hours.
The further preferred step（1）Roasting condition include：Temperature is 350-650 DEG C, and the time is 2-10 hours.
It is preferred that the step（2）By step（1）Obtained product of roasting and at least one boehmite or a false water are soft
In the mixture that aluminium stone and water are mixed to get, solid content in mass is 1%-80%, wherein, the product of roasting with dry
The mass ratio of the boehmite of base meter or false boehmite is 0.1-20.The further preferred step（2）By step
（1）In the mixture that obtained product of roasting is mixed to get with least one boehmite or false boehmite and water,
Solid content in mass is 5%-70%, wherein, the product of roasting and the boehmite in terms of butt or the soft aluminium of a false water
The mass ratio of stone is 0.2-12.
When the water content in described mixture is enough to make the mixture be slurries（For example, solid content in mass
For less than 35%）When, in the step（4）Drying before preferably include filtering the step of.
The preferable step（3）Hydrothermal conditions include：Temperature is extremely less than 140 DEG C for 60 DEG C, time 0.5-
48 hours.The further preferred step（3）Hydrothermal conditions include：Temperature is 80-120 DEG C, and the time is that 4-24 is small
When.Either, the preferable step（3）Hydrothermal conditions include：Temperature is to being less than or equal to more than or equal to 140 DEG C
250 DEG C, the time is 0.5-48 hours；The further preferred step（3）Hydrothermal conditions include：Temperature is 150-
220 DEG C, the time is 4-24 hours.
It is preferred that the step（4) drying temperature is 60 DEG C -180 DEG C, and drying time is -24 hours 0.5 hour.Enter one
The step preferably step（4) drying temperature is 80 DEG C -150 DEG C, and drying time is -12 hours 1 hour.
In the present invention, the hydrated alumina is in hibbsite, false boehmite, boehmite
It is one or more of.
Wherein, the hibbsite includes gibbsite（α-Al2O3·3H2O）, surge aluminium stone（β1- Al2O3·
3H2O）With promise diaspore（β2-Al2O3·3H2O）.
The false boehmite is also known as boehmite, is characterized with X-ray diffraction, to be a kind of at 14.5 ° ± 0.5 °（2
θ）Occur wide and disperse（020）The hydrated alumina of crystallographic plane diffraction peak.
The boehmite is also known as boehmite, is characterized with X-ray diffraction, to be a kind of at 14.5 ° ± 0.5 °（2θ）Go out
It is now most strong, narrow and sharp（020）The hydrated alumina of crystallographic plane diffraction peak（Boehmite at 45.8 °, 51.6 ° and
55.2 ° correspond to respectively（131）、（220）With（151）Diffraction maximum not available for the false boehmite of crystal face）.
Inventors of the present invention have surprisingly found that boehmite and/or false boehmite are passed through with one or more of
300 DEG C of -950 DEG C of roastings（Heat treatment）0.5-24 hours, preferably it is calcined through 300 DEG C -750 DEG C（Heat treatment）1-24 hours, enter one
Step is preferably calcined through 350 DEG C -650 DEG C（Heat treatment）Hydrated alumina and the water mixing of 2-10 hours, obtains a kind of mixing
Thing, and by the mixture in closed container in 60 DEG C of -250 DEG C of hydro-thermal process 0.5-48 hours, be preferable over 80-220 DEG C of hydro-thermal
4-24 hours are handled, thus the relative crystallinity of modified obtained boehmite and/or false boehmite improves, and thus
Fired obtained aluminum oxide maintains higher specific surface area and pore volume.
In the present invention, when it is more than 140 DEG C to control hydro-thermal process temperature, gained modified product is boehmite；Control
When hydro-thermal process temperature processed is less than 140 DEG C, crystalline phase and the initiation material of products therefrom are consistent.
In a detailed embodiment, the crystalline phase of the modified product step consistent with initiation material is preferably made
Suddenly（3）Hydrothermal conditions include：Temperature is 60 DEG C and is extremely less than 140 DEG C, and the time is 0.5-48 hours；Further preferred
The step（3）Hydrothermal conditions include：Temperature is 120 DEG C of 80-, and the time is 1-24 hours.
In another embodiment, the step that the modified product is boehmite is preferably made（3）
Hydrothermal conditions include：Temperature is that the time is 0.5-48 hours more than or equal to 140 DEG C to being less than or equal to 250 DEG C；Further
The preferable step（3）Hydrothermal conditions include：Temperature is 150-220 DEG C, and the time is 4-24 hours.
In the present invention, the boehmite, false boehmite and gibbsite can be commercially available commodity, can also
It is to be prepared using arbitrary prior art, this is not particularly limited.
It is being enough the hydrated alumina in 300 DEG C of -950 DEG C of roastings（Heat treatment）1-24 hours, preferably through 300
DEG C of -750 DEG C roastings（Heat treatment）1-24 hours, further preferably it is calcined through 350 DEG C -650 DEG C（Heat treatment）The bar of 2-10 hours
Under part, the present invention is to step（1）Described method of roasting is not particularly limited.For example, it may be by the hydrated alumina
It is calcined in usual baking oven or roaster under air atmosphere or in the baking oven or roaster of vacuum-pumping
Under vacuum or it is passed through under inert gas conditions and carries out.When the roasting is passed through inert gas, the inert gas can
To be the not oxygen-containing gas for being arbitrarily enough to gasify under the roasting condition, for example, can be selected from nitrogen, argon gas, helium,
One or more in carbon dioxide and water vapour.
Butt in the present invention refers to：A certain amount of hydrated alumina in air atmosphere in Muffle furnace with 4 DEG C/
Minute heating rate be raised to 600 DEG C, then in 600 DEG C of constant temperature 4 hours, the oxidation before the weight of product and roasting after roasting
The percentage of the weight ratio of aluminium hydrate, the weight of the hydrated alumina before the weight ÷ of product is calcined after butt=roasting
Amount × 100%.
In the present invention, the closed reactor can be the reactor of the arbitrarily achievable hydro-thermal reaction, for example,
Autoclave etc., the reaction can be carried out under static conditions, also be carried out under stirring, preferably under stirring
Carry out hydro-thermal process.
In the present invention, contain R in the aluminum oxide article shaped1R2R3R4N+X-, wherein, the R1R2R3R4N+X-Quality
Fraction is 0.1%-10%, preferably 0.3%-5%.R therein1R2R3R4N+X-Selected from primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium
One or more in salt.For example, selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl
Amine hydrochlorate, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, octadecyl
Trimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride,
Didodecyldimethylammbromide bromide, double dodecyl dimethyl ammonium chlorides, double dodecyldimethylamine base ammonium bromides, double tetradecanes
Base alkyl dimethyl ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, trimethyl bromine
Change the one or more of ammonium and DTAC, or selected from ethanolamine salt and dococylpyridinium hydrochloride and
Their mixture etc..
Wherein, as the R1R2R3R4N+X-For primary amine salt when, the R1、R2、R3Or R4In one kind be selected from hydrocarbon substituent or
The substituent of hydrocarbon derivative, other are hydrogen；As the R1R2R3R4N+X-For secondary amine salt when, the R1、R2、R3Or R4In two kinds
Substituent selected from hydrocarbon substituent and/or hydrocarbon derivative, other are hydrogen；As the R1R2R3R4N+X-For tertiary ammonium salt when, the R1、
R2、R3Or R4In three kinds of substituents selected from hydrocarbon substituent and/or hydrocarbon derivative, another is hydrogen；As the R1R2R3R4N+X-
For quaternary amine when, the R1、R2、R3Or R4In four kinds of substituents selected from hydrocarbon substituent and/or hydrocarbon derivative.Wherein, when
When having two or more derivatives for hydrocarbon substituent and/or hydrocarbon substituent in R1, R2, R3 and R4, they can with it is identical can also
It is different.
The hydrocarbon substituent is selected from C1-C20 straight or branched alkyl, preferably C1-C18 straight or branched alkane
Base, for example, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, TTAB, the tetradecane
Base trimethyl ammonium chloride, DTAB, DTAC, octadecyl trimethyl bromination
Ammonium, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, double dodecyls
Ditallowdimethyl ammonium bromide, double dodecyl dimethyl ammonium chlorides, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine base chlorine
Change ammonium, DDA, dioctadecyl dimethyl ammonium chloride；The either cycloalkyl selected from C3-C20,
Preferably C6-C18 cycloalkyl, for example, cycloalkyl imidazoline quaternary ammonium salt；The either aryl selected from C6- C20, it is preferably
C6-C18 aryl, for example, dodecyl benzyl dimethyl ammonium chloride, lauryl isoquinolinium bromide salt；The hydrocarbon spreads out
The substituent of biology is selected from the alkyl with hydroxyl and/or heterocyclic substituent, as the example of the substituent of the derivative of hydrocarbon, such as
Dococylpyridinium hydrochloride, glycidyl dodecyl dimethyl ammonium chloride, benzethonium chloride.
The X is selected from iodine, preferably chlorine or bromine.
It is being enough to make to contain 0.1%-10%, preferably 0.3%-5% R in the article shaped1R2R3R4N+X-On the premise of, this
The method that invention introduces to it does not limit.
In a specific embodiment, R is introduced in the article shaped1R2R3R4N+X-Method, including：（1）With
Containing R1R2R3R4N+X-Solution impregnate the article shaped, the ratio between the volume of the maceration extract and pore volume of the article shaped are
0.5-20, preferably 1-15；（2）The mixture that dipping obtains is heat-treated in closed reactor, heat treatment temperature is
Room temperature is to 250 DEG C, preferably 60 DEG C -220 DEG C, and the time is -48 hours 0.5 hour, preferably -36 hours 1 hour；（3）Dry
Step（2）Product, the drying condition includes：Temperature is 40 DEG C -250 DEG C, and preferably 100 DEG C -180 DEG C, the time is 1 small
When -24 hours, preferably -18 hours 2 hours.
In the present invention, room temperature can be the indoor temperature in interior each season throughout the year, generally 5-40 DEG C.
In the present invention, the solvent of the maceration extract is selected from water and/or alcohol（Such as ethanol）.
The R in being enough to make the finally article shaped1R2R3R4N+X-Content meet require on the premise of, the present invention to dipping
R in liquid1R2R3R4N+X-Content and dipping time be not particularly limited.In specific implementation, preferred rate-determining steps（1）In
R in the maceration extract1R2R3R4N+X-Be 0.01-10 with the weight ratio of aluminum oxide article shaped：100, more preferably
0.1-8：100, more preferably 0.3- 5：100.
In the case where being enough to ensure that the heat treatment is carried out under air tight condition, the present invention does not have to the closed reactor
There are special limitation, common such as autoclave high-pressure reactor.
In the present invention, R is introduced in the aluminum oxide article shaped1R2R3R4N+X-Method in, step（3）Dry purpose
In the solvent in impregnation product is removed, on the premise of being enough to realize the purpose, the present invention does not have to the method for the drying
Limitation, such as can be the method for heat drying or vacuum drying method.
In the present invention, the aluminum oxide can contain selected from silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, oxygen
Change one or more of adjuvant components in beryllium, wherein, the mass fraction of the adjuvant component is less than 10%, is preferably 0.3%-
5%。
When in the article shaped contain in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide one
Kind or during several adjuvant components, the preparation process of the article shaped include introducing be selected from silica, titanium oxide, magnesia,
The step of one or more of adjuvant components in zirconium oxide, thorium oxide, beryllium oxide, the method for introducing adjuvant component are conventional
Method.For example, it may be by containing one kind in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide or several
Plant one or more of mixtures warps in the hibbsite, monohydrate alumina and amorphous hydroted alumina of adjuvant component
It is made after being molded and being calcined.Can also aluminum oxide and/or its precursor will be mixed with the compound containing adjuvant component, afterwards
Obtained through shaping, drying and roasting.
In the present invention, clay and/or molecular sieve can be contained in the article shaped, wherein, the clay and/or molecule
The mass fraction of sieve is less than 35%, preferably 1%-20%.
When containing clay and/or molecular sieve in the article shaped, include introducing in the preparation process of the article shaped
The step of clay and/or molecular sieve, the method thing conventional method for introducing clay and/or molecular sieve.For example, by the clay
And/or molecular sieve and the one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina
Mixture after shaping and roasting be made.
In the present invention, the clay can be selected from kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite,
One or more in rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.The molecular sieve can be zeolite molecules
Sieve and/or non-zeolite molecular sieve.The zeolite molecular sieve can be erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite,
ZSM-11 zeolites, ZSM-22 zeolites, ZSM-23 zeolites, ZSM-35 zeolites, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecules
Sieve, ZSM-4 molecular sieves, ZSM-18 molecular sieves, ZSM-20 molecular sieves, ZSM-48 zeolites, ZSM-57 zeolites, faujasite, Beta
One or more in zeolite and omega zeolite.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, HTS and phosphoric acid
Sial（That is, SAPO）One or more in molecular sieve.According to the present invention, the molecular sieve is preferably hydrogen type molecular sieve.It is described
Hydrogen type molecular sieve can also use conventional method to prepare with commercially available.For example, can be conventional by sodium form molecular sieve
Ammonium ion exchange process carries out ion exchange and drying, forms ammonium type molecular sieve, then fired formation hydrogen type molecular sieve.
Usually, it is provided by the invention to contain R1R2R3R4N+X-Aluminum oxide article shaped can be used as adsorbent or catalyst carrier
Use.Further study showed that provided by the invention contain R1R2R3R4N+X-Aluminum oxide article shaped be particularly suitable as carrier use
In preparing loaded catalyst, such as hydrogenation catalyst etc..
For example, contain R with provided by the invention respectively1R2R3R4N+X-Aluminum oxide article shaped and conventional method prepare carrier
Prepare tenor 2.4%NiO and 12%MoO3Catalyst C and DC（Reference agent）.With containing 4,6- dimethyl Dibenzothiophenes
（4,6-DMDBT）The mixed solution of 0.59 weight % n-decane is raw material, and the hydrodesulfurization activity of two kinds of catalyst is carried out
Evaluation.Using catalyst DC activity as 100, catalyst C hydrodesulfurization activity is 112.As a result show, provided with prior art
Catalyst prepared by carrier is compared, and the hydrodesulfurization activity that catalyst is prepared by present invention offer carrier significantly improves.
Embodiment
The present invention will be further illustrated in following example, but not thereby limiting the invention.
Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometers are used in following examples, to catalysis
The content of each element carries out analysis measure in agent.
The measure reference of sample crystalline phase, relative crystallinity and mean grain size《Solid catalyst Practical Research method》（Liu
The big volume of Wei Qiao, Sun Gui, Sinopec publishing house, 2000,57-89）With《Petrochemical Engineering Analysis method（RIPP test methods）》（Poplar
Kingfisher is fixed, and Gu Kanying, Wu Wenhui are compiled, Science Press, and 1990,394-405）In X-ray diffraction method carry out.
Embodiment 1-10 illustrates the modification boehmite of the invention used and/or false boehmite, its preparation method
And the aluminum oxide thus prepared.
The hydrated alumina used in experiment is：
CL-A powder（False boehmite powder）, relative crystallinity 100%, grain size 2.9nm, the weight % of butt 70, purchase
From sinopec Chang Ling catalyst branch company.
CL-B powder（Boehmite）, relative crystallinity 100%, grain size 5.2nm, the weight % of butt 78, in being purchased from
Petrochemical industry Chang Ling catalyst branch company）.
CL-C powder（Gibbsite（α-Al2O3·3H2O））, relative crystallinity 100%, grain size 156nm, butt 65
Weight %, purchased from sinopec Chang Ling catalyst branch company.
Wherein, 10000 grams of CL-A powder are weighed, use banded extruder（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, type
Number：F-26(Ⅲ)）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C are dried 4 hours, in air
Under atmosphere in Muffle furnace 600 DEG C of constant temperature 4 hours, obtain alumina support CL-A-Al2O3.Characterized by X-ray diffraction method
Its crystalline phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, knot
Fruit is listed in Table 2 below.
10000 grams of CL-B powder are weighed, use banded extruder（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F-
26(Ⅲ)）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C are dried 4 hours, in air atmosphere
Under in Muffle furnace 600 DEG C of constant temperature 4 hours, obtain alumina support CL-B-Al2O3.It is brilliant that it is characterized by X-ray diffraction method
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, as a result arranges
In table 2.
According to the step in the method provided by the present invention（1）Obtained product of roasting is：
CL-A-600：10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-A-600 is obtained to 600 DEG C, and in 600 DEG C of constant temperature within 4 hours.
CL-A-450：10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 3 DEG C/min of heating rate liter
CL-A-450 is obtained to 450 DEG C, and in 450 DEG C of constant temperature within 4 hours.
CL-A-400：10000 grams of CL-A powder are weighed in a nitrogen atmosphere in Muffle furnace with 5 DEG C/min of heating rate liter
CL-A-400 is obtained to 400 DEG C, and in 400 DEG C of constant temperature within 4 hours.
CL-A-350：10000 grams of CL-A powder are weighed to be raised to 3 DEG C/min of heating rate in baking oven in a nitrogen atmosphere
350 DEG C, and obtain CL-A-350 within 4 hours in 350 DEG C of constant temperature.
CL-B-600：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-600 is obtained to 600 DEG C, and in 600 DEG C of constant temperature within 4 hours.
CL-B-450：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-450 is obtained to 450 DEG C, and in 450 DEG C of constant temperature within 4 hours.
CL-B-400：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-400 is obtained to 400 DEG C, and in 400 DEG C of constant temperature within 4 hours.
CL-B-350：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-350 is obtained to 350 DEG C, and in 350 DEG C of constant temperature within 4 hours.
CL-C-600：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 600 DEG C, and obtains CL-C-600 within 4 hours in 600 DEG C of constant temperature.
CL-C-450：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 450 DEG C, and obtains CL-C-450 within 6 hours in 450 DEG C of constant temperature.
CL-C-400：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 400 DEG C, and obtains CL-C-400 within 6 hours in 400 DEG C of constant temperature.
CL-C-350：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 350 DEG C, and obtains CL-C-350 within 6 hours in 350 DEG C of constant temperature.
Embodiment 1
120 grams of 350 grams of CL-A powder, the CL-A-600 powder in terms of butt is weighed respectively（CL-A-600 powder and the CL- in terms of butt
The mass ratio of A powder is 0.34）, they are mixed into slurries with 3600 grams of deionized waters；The slurries are transferred into band to stir
The volume mixed is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, and 160 DEG C, and constant temperature 4 under agitation are heated to after closed
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, obtains modified product Q-S1.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S1 banded extruders（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F- 26(Ⅲ)）It is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.Wet bar is after 120 DEG C are dried 4 hours, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S1.Its crystalline phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 2
300 grams of 224 grams of CL-A powder, the CL-A-600 powder in terms of butt is weighed respectively（CL-A-600 powder with terms of butt
The mass ratio of CL-A powder is 1.34）, they are mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
The volume of stirring is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S2.Penetrated by X-
Line diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S2 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.
Embodiment 3
464 grams of 109 grams of CL-A powder, the CL-A-600 powder in terms of butt is weighed respectively（CL-A-600 powder with terms of butt
The mass ratio of CL-A powder is 4.25）, they are mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
The volume of stirring is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S3.Penetrated by X-
Line diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
Formed alumina provided by the invention and its preparation：
By Q-S3 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.
Embodiment 4
150 grams of 100 grams of 84 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively
250 grams of powder, 180 grams of CL-A-600 powder（The total amount and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be
8.10）, they are mixed into slurries with 3600 grams of deionized waters；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours；Room temperature and after filtering is down to, will
Filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S4.It is brilliant that it is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S4 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.
Embodiment 5
200 grams of 100 grams of 140 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A- in terms of butt are weighed respectively
450 300 grams of powder, 10 grams of CL-A-600 powder（The total amount and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be
4.36）, they are mixed into slurries with 3100 grams of deionized waters；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, 60 DEG C of constant temperature is heated to after closed 48 hours；Room temperature and after filtering is down to, will
Filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S5.It is brilliant that it is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S5 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.
Embodiment 6
100 grams of 200 grams of 70 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A- in terms of butt are weighed respectively
450 400 grams of powder, 20 grams of CL-A-600 powder（The total amount and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be
10.29）, they are mixed into slurries with 3200 grams of deionized waters；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, 100 DEG C of constant temperature is heated to after closed 24 hours；Room temperature and after filtering is down to,
Filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S6.It is characterized by X-ray diffraction method
Crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S6 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.
Embodiment 7
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder
220 grams, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, CL-C-600
8 grams of powder（The total amount of the powder of CL- 350~600 and the mass ratio for the CL powder counted using butt is 8.09）, they and 3600 grams are gone
Ionized water is mixed into slurries；The slurries are transferred to the height for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters
Press in kettle, 160 DEG C of constant temperature is heated to after closed 4 hours；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C,
Obtain modified hydrated alumina Q-S7.It is big that its crystalline phase, relative crystallinity and crystal grain are characterized by X- Diffractions
Small, the results are shown in Table 1.
By Q-S7 banded extruders（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F- 26(Ⅲ)）It is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.Wet bar is after 120 DEG C are dried 4 hours, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S7.Its crystalline phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 8
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder
220 grams, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, CL-C-600
8 grams of powder（The total amount of the powder of CL- 350~600 and the mass ratio for the CL powder counted using butt is 8.09）, they and 3600 grams are gone
Ionized water is mixed into slurries；The slurries are transferred to the height for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters
Press in kettle, 160 DEG C of constant temperature is heated to after closed 4 hours.After being down to room temperature, high pressure kettle cover is opened, adds 11.75 grams of di(2-ethylhexyl)phosphates
Hydrogen ammonium, continue stirring 24 hours in room temperature, after filtering, filter cake is dried 8 hours in 120 DEG C, modified containing is obtained and helps
The hydrated alumina Q-S8 of agent phosphorus.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, tied
Fruit is listed in Table 1 below.
By Q-S8 banded extruders（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F- 26(Ⅲ)）It is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.Wet bar is after 120 DEG C are dried 4 hours, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S8.Its crystalline phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, and the results are shown in Table 2.Using X
The content of fluorescence spectrometry adjuvant component, the mass fraction for the phosphate builder counted using element is 0.41%.
Embodiment 9
300 grams of 224 grams of CL-A powder, the CL-A-600 powder in terms of butt is weighed respectively（CL-A-600 powder with terms of butt
The mass ratio of CL-A powder is 1.34）, they are mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
The volume of stirring is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, adds 84.51 grams of titanium sulfates, continues stirring 24 hours, then filters.By filter cake through 120 DEG C
Dry 8 hours, obtain the modified hydrated alumina Q-S9 containing auxiliary agent titanium.It is brilliant that it is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S9 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measure
Its specific surface area and pore volume, the results are shown in Table 2.Using the content of X-fluorescence method measure adjuvant component, the titanium in terms of element
The mass fraction of auxiliary agent is 3.12%.
Embodiment 10
320 grams of 230 grams of CL-B powder, the CL-A-450 powder in terms of butt is weighed respectively（CL-A-600 powder and the CL- in terms of butt
The mass ratio of B powder is 1.39）, they are mixed into slurries with 3600 grams of deionized waters；The slurries are transferred into band to stir
The volume mixed is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, and 200 DEG C, and constant temperature 4 under agitation are heated to after closed
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, obtains modified product Q-S10.It is logical
Cross X-ray diffraction method and characterize its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S10 banded extruders（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F- 26(Ⅲ)）It is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.Wet bar is after 120 DEG C are dried 4 hours, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S10.Its crystalline phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 11-13 illustrates the modification of the modified boehmite of routine and/or false boehmite that the present invention uses
Aluminum oxide prepared by method and modifier therefrom.
Embodiment 11
470 grams of the CL-A powder in terms of butt is weighed, itself and 3600 grams of deionized waters are mixed into slurries；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 160 DEG C of constant temperature 4 is heated to after closed
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina QBF-1.
Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
By QBF-1 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S11 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, the results are shown in Table 2.
Embodiment 12
470 grams of CL-A-600 powder are weighed, itself and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred to
Volume with stirring is in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours；Drop
To room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina QBF-2.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By QBF-2 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S12 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, the results are shown in Table 2.
Embodiment 13
470 grams of the CL-B powder in terms of butt is weighed, itself and 3600 grams of deionized waters are mixed into slurries；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 200 DEG C of constant temperature 4 is heated to after closed
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina QBF-3.
Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
By QBF-3 banded extruders（With embodiment 1）It is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S13 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, the results are shown in Table 2.
Table 1
Wherein, when determining the crystallinity of false boehmite, using CL-A powder as standard specimen；In the knot of measure boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When determining gama-alumina crystallinity, with CL-B-Al2O3Thing standard specimen.
Table 2
| Embodiment | Aluminum oxide | Specific surface area, m2/g | Pore volume, cm3/g |
| CL-A-Al2O3 | 283 | 0.71 | |
| CL-B-Al2O3 | 201 | 0.51 | |
| 1 | S1 | 255 | 0.66 |
| 2 | S2 | 238 | 0.62 |
| 3 | S3 | 213 | 0.61 |
| 4 | S4 | 236 | 0.62 |
| 5 | S5 | 265 | 0.68 |
| 6 | S6 | 258 | 0.66 |
| 7 | S7 | 216 | 0.60 |
| 8 | S8 | 222 | 0.61 |
| 9 | S9 | 243 | 0.63 |
| 10 | S10 | 185 | 0.60 |
| 11 | S11 | 233 | 0.52 |
| 12 | S12 | 173 | 0.60 |
| 13 | S13 | 131 | 0.45 |
Embodiment 14-29 illustrates provided by the invention containing R1R2R3R4N+X-Aluminum oxide article shaped and preparation method thereof.
Embodiment 14
Weigh 1200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.36 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 90 DEG C of constant temperature 24 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S1.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 15
Weigh 2200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.85 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after placement 48 hours at room temperature.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S2.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 16
Weigh 3200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 3.81 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 60 DEG C of constant temperature 18 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S3.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 17
Weigh 4200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.10 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 120 DEG C of constant temperature 6 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S4.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 18
Weigh 5200 grams of carrier S to be placed in autoclave, add the aqueous solution containing 0.89 gram of cetyl trimethylammonium bromide
It is 200 milliliters, closed after 160 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing R1R2R3R4N+
X-Aluminum oxide article shaped R-S5.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 19
Weigh 6200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 4.86 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 180 DEG C of constant temperature 2 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S6.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 20
Weigh 7200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 5.18 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 110 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S7.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 21
Weigh 8200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 4.56 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed after 120 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S8.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 22
Weigh 9200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 4.69 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed to be handled 4 hours after 130 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S9.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 23
Weigh 10200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.02 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed to be handled 10 hours after 80 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S10.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 24
Weigh 11200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.36 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed to be handled 24 hours after 90 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S11.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 25
Weigh 12200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.36 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed to be handled 24 hours after 90 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S12.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 26
Weigh 13200 grams of carrier S to be placed in autoclave, add the anhydrous second containing 1.36 grams of cetyl trimethylammonium bromides
200 milliliters of alcoholic solution, it is closed to be handled 4 hours after 90 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, contained
R1R2R3R4N+X-Aluminum oxide article shaped R-S13.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 27
Weigh support C L-A-Al2O3200 grams are placed in autoclave, add containing 1.36 grams of cetyl trimethylammonium bromides
200 milliliters of ethanol solution, it is closed to be handled 24 hours after 90 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, obtained
Contain R1R2R3R4N+X-Aluminum oxide article shaped R-S14.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 28
Prepare with the hydrated alumina Q-S2 powder of the equivalent of embodiment 2, then with 25 grams of silicon dioxide powders（Purchased from sinopec
Chang Ling catalyst branch company）Banded extruder is used after mixing（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26
(Ⅲ)）It is 1.6 millimeters of cloverleaf pattern bar to be extruded into circumscribed circle diameter, and 4 hours are dried through 120 DEG C, finally horse in air atmosphere
600 DEG C not are raised to 4 DEG C/min of heating rate in stove, then in 600 DEG C of constant temperature 4 hours, obtains alumina support S14.
Weigh 14200 grams of carrier S to be placed in autoclave, addition contains 3.56 grams of cetyl trimethylammonium bromides and 3.89 grams
200 milliliters of the ethanol solution of DTAC, it is closed to be handled 2 hours after 100 DEG C.By sample after cooling
Dry 4 hours, obtained containing R in 120 DEG C1R2R3R4N+X-Aluminum oxide article shaped R-S15.R in article shaped1R2R3R4N+X-Matter
Amount fraction is listed in table 3.
Embodiment 29
Prepare with the hydrated alumina Q-S2 powder of the equivalent of embodiment 2, then with 36 grams of Hydrogen Y molecular sieves（Na2O content
0.2%, cell parameter 2.464, relative crystallinity 88%, purchased from sinopec Chang Ling catalyst branch company）Banded extruder is used after mixing（It is raw
Produce producer：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26(Ⅲ)）It is extruded into the clover that circumscribed circle diameter is 1.6 millimeters
Shape bar, dried 4 hours through 120 DEG C, be finally raised to 600 DEG C in Muffle furnace with 4 DEG C/min of heating rate in air atmosphere,
Then in 600 DEG C of constant temperature 4 hours, alumina support S15 is obtained.
15200 grams of carrier S is weighed to be placed in autoclave, add containing 1.73 grams of cetyl trimethylammonium bromides, 1.12 grams
Hexadecyltrimethylammonium chloride, 3.08 grams of DTABs and 3.16 grams of DTACs
200 milliliters of ethanol solution, it is closed to be handled 3 hours after 100 DEG C.Sample is dried 4 hours in 120 DEG C after cooling, obtained
Contain R1R2R3R4N+X-Aluminum oxide article shaped R-S16.R in article shaped1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 30-45 illustrates the hydrogenation catalyst prepared with carrier provided by the invention.
Implemented respectively with 199 milliliters of dippings of ammonia spirit containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates
R-S1, R-S2 that example 14~29 is prepared, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8, R-S9, R-S10, R-S11,
R-S12, R-S13, R-S14, R-S15 and R-S16, dip time 2 hours, impregnation product is dry 4 hours in 120 DEG C afterwards, obtains
To catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and C16.
Comparative example 1-4 illustrates comparative catalyst and its preparation.
Comparative example 1
11200 grams of carrier S is weighed, by the carrier S 11 with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates
199 milliliters of ammonia spirit impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst D1.
Comparative example 2
12200 grams of carrier S is weighed, by the carrier S 12 with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates
199 milliliters of ammonia spirit impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst D2.
Comparative example 3
13200 grams of carrier S is weighed, by the carrier S 13 with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates
199 milliliters of ammonia spirit impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst D3.
Comparative example 4
Weigh support C L-A-Al2O3200 grams, by support C L-A-Al2O3With containing 34.96 grams of ammonium heptamolybdates, 22.62 grams
199 milliliters of the ammonia spirit of Nickelous nitrate hexahydrate impregnates above-mentioned carrier 2 hours, then dries 4 hours, is catalyzed at 120 DEG C
Agent D4.
Catalyst performance evaluation：
The hydrodesulfurization performance that embodiment 30-45 provides the comparative catalyst that catalyst and comparative example 1-4 are provided is evaluated,
As a result it is listed in table 3.
Evaluating catalyst is with dimethyl Dibenzothiophene containing 4,6-（4,6-DMDBT）The mixing of 0.59 weight % n-decane
Solution is raw material, in high-pressure micro-device（Manufacturer：Beijing petrochemical industry information automation company, model：DADI）Upper evaluation is urged
The hydrodesulfurization activity of agent, the particle by catalyst breakage into a diameter of 40-60 mesh, the loadings of catalyst are 0.15 gram.
Before formal charging, presulfurization, pre- sulphur first are carried out to catalyst respectively using the hexamethylene containing 6 weight % carbon disulfide as sulfurized oil
The condition of change includes：Pressure is 4.14MPa, and temperature is 362 DEG C, and the time is 3.5 hours, sulfurized oil feed rate is 0.2 milliliter/
Minute.After vulcanization terminates, reaction temperature is cooled to as 280 DEG C, cuts raw material.Reaction condition includes：Raw material feed rate is 0.2
Ml/min, pressure 4.14MPa, hydrogen to oil volume ratio 900.Reaction samples after 3 hours in high-pressure separator exit.Institute
Sample is obtained to be analyzed with Agilent6890N gas chromatographs.Wherein, 4,6-DMDBT hydrodesulfurization activity A is counted as the following formula
Calculate：
A=ln [100/ (100-X)],
In formula, X 4,6-DMDBT desulfurization degree（X circular referring to《It is catalyzed journal》, 2002,23（3）：
271-275）.
The hydrodesulfurization activity for taking comparative catalyst D1 4,6-DMDBT is 100, then relative the 4,6- of other catalyst
DMDBT hydrodesulfurization activity can be represented by the formula：
Relative activity=(AQT/AD1) × 100%, A in formulaQTFor the activity of other catalyst, AD1For the work of reference catalyst
Property.
Table 3
Shown by the result of table 3, higher hydrodesulfurization activity is shown according to the hydrogenation catalyst of the present invention.
Claims (26)
1. one kind contains R1R2R3R4N+X-Aluminum oxide article shaped, contain R1R2R3R4N+X-, it is described on the basis of the article shaped
R1R2R3R4N+X-Mass fraction be 0.1%-10%, the R1R2R3R4N+X-Selected from primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt
In one or more, wherein the R1、R2、R3、R4Selected from hydrogen, hydrocarbon substituent and its derivative；
R is introduced in the aluminum oxide article shaped1R2R3R4N+X-Method include：（1）With containing R1R2R3R4N+X-Solution dipping
The ratio between pore volume of the aluminum oxide article shaped, the volume of the maceration extract and the article shaped is 0.5-20；（2）It will impregnate
To mixture place in room temperature or be heat-treated in closed reactor, heat treatment temperature is room temperature to 250 DEG C, and the time is
- 48 hours 0.5 hour；（3）Drying steps（2）Product, the drying condition includes：Temperature is 40 DEG C -250 DEG C, the time 1
- 24 hours hours.
2. article shaped according to claim 1, it is characterised in that on the basis of the article shaped, the R1R2R3R4N+X-
Mass fraction be 0.3%-5%.
3. article shaped according to claim 1, it is characterised in that the hydrocarbon substituent is selected from C1-C20 straight or branched
Alkyl, or the cycloalkyl selected from C3-C20, or the aryl selected from C6-C20；The derivative of the hydrocarbon substituent is selected from
Alkyl with hydroxyl and/or heterocyclic substituent.
4. article shaped according to claim 3, it is characterised in that the hydrocarbon substituent is selected from C1- C18 straight chain or branch
Alkyl group；The either cycloalkyl selected from C6-C18；The either aryl selected from C6-C18.
5. according to the article shaped described in claim 1,2 or 3 any one, it is characterised in that the X is selected from chlorine, bromine or iodine.
6. article shaped according to claim 5, it is characterised in that the X is selected from chlorine or bromine.
7. according to the article shaped described in claim 1,2 or 3 any one, it is characterised in that the R1R2R3R4N+X-Selected from 16
Alkyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, 14
Alkyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorination
Ammonium, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecanes
Base alkyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double octadecyldimethyls
Ammonium bromide, dioctadecyl dimethyl ammonium chloride, the one of DTAB and DTAC
Kind is a variety of.
8. according to the article shaped described in claim 1,2 or 3 any one, it is characterised in that the R1R2R3R4N+X-Selected from ethanol
Amine salt, dococylpyridinium hydrochloride.
9. article shaped according to claim 1, it is characterised in that in the article shaped contain selected from silica, titanium oxide,
One or more of adjuvant components in magnesia, zirconium oxide, thorium oxide, beryllium oxide, on the basis of the article shaped, the auxiliary agent
The mass fraction of component is less than 10%.
10. article shaped according to claim 9, it is characterised in that on the basis of the article shaped, the adjuvant component
Mass fraction is 0.3%-5%.
11. the article shaped according to claim 1 or 9, it is characterised in that contain clay and/or molecule in the article shaped
Sieve, on the basis of the article shaped, the mass fraction of the clay and/or molecular sieve is less than 35%.
12. article shaped according to claim 11, it is characterised in that on the basis of the article shaped, the clay and/or
The mass fraction of molecular sieve is 1%-20%.
13. one kind contains R1R2R3R4N+X-Aluminum oxide article shaped preparation method, be included in the aluminum oxide article shaped and draw
Enter R1R2R3R4N+X-, on the basis of the article shaped, the R1R2R3R4N+X-Introduction volume make in the article shaped
R1R2R3R4N+X-Mass fraction is 0.1%-10%, the R1R2R3R4N+X-In primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt
One or more, wherein the R1、R2、R3、R4Derivative or hydrogen selected from hydrocarbon substituent, hydrocarbon substituent；
It is described to introduce R in the aluminum oxide article shaped1R2R3R4N+X-Method, including：（1）With containing R1R2R3R4N+X-Solution
Impregnate the aluminum oxide article shaped, the ratio between the volume of the maceration extract and pore volume of the article shaped are 0.5-20；（2）Will leaching
The mixture that stain obtains is placed in room temperature or is heat-treated in closed reactor, heat treatment temperature be room temperature to 250 DEG C, when
Between be -48 hours 0.5 hour；（3）Drying steps（2）Product, the drying condition includes：Temperature is 40 DEG C -250 DEG C, when
Between be -24 hours 1 hour.
14. according to the method for claim 13, it is characterised in that on the basis of the article shaped, the R1R2R3R4N+X-
Introduction volume make R in the article shaped1R2R3R4N+X-Mass fraction be 0.3%-5%.
15. according to the method for claim 13, it is characterised in that the hydrocarbon substituent is selected from C1-C20 straight or branched
Alkyl, or the cycloalkyl selected from C3-C20, or the aryl selected from C6-C20；The derivative of the hydrocarbon substituent is selected from
Alkyl with hydroxyl and/or heterocyclic substituent.
16. according to the method for claim 15, it is characterised in that the substituent of the hydrocarbon is selected from C1-C18 straight chain or branch
Alkyl group；The either cycloalkyl selected from C6-C18；The either aryl selected from C6-C18.
17. according to the method described in claim 13,14 or 15 any one, it is characterised in that the X is selected from chlorine, bromine or iodine.
18. according to the method described in claim 13,14 or 15 any one, it is characterised in that the R1R2R3R4N+X-Selected from ten
Six alkyl trimethyl ammonium bromides, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, ten
Tetraalkyl trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorine
Change ammonium, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double 12
Alkyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double hexadecyldimethylamines
Base ammonium bromide, dioctadecyl dimethyl ammonium chloride, DTAB and DTAC
It is one or more.
19. according to the method described in claim 13,14 or 15 any one, it is characterised in that the R1R2R3R4N+X-Selected from second
Alcohol amine salt, dococylpyridinium hydrochloride.
20. according to the method for claim 13, it is characterised in that be included in the process in the article shaped and introduce
The step of one or more of adjuvant components in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, with
On the basis of the article shaped, the introduction volume of the adjuvant component make the mass fraction of adjuvant component in the article shaped for 10% with
Under.
21. according to the method for claim 20, it is characterised in that on the basis of the article shaped, the adjuvant component
Mass fraction is 0.3%-5%.
22. the method according to claim 13 or 20, it is characterised in that contain clay and/or molecule in the article shaped
Sieve, on the basis of the article shaped, the mass fraction of the clay and/or molecular sieve is less than 35%.
23. according to the method for claim 22, it is characterised in that on the basis of the article shaped, the clay and/or point
The mass fraction of son sieve is 1%-20%.
24. according to the method for claim 13, it is characterised in that step（1）Described in maceration extract volume with it is described into
The ratio between pore volume of type thing is 1-15；Step（2）Described in heat treatment temperature be 60 DEG C to 220 DEG C, the time is 1 hour -36 small
When, step（3）Drying condition include：Temperature is 100 DEG C -180 DEG C, and the time is -18 hours 2 hours.
25. according to application of any one of the claim 1-12 article shapeds as adsorbent.
26. according to application of any one of the claim 1-12 article shapeds as catalyst carrier.
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