CN104971732B - A kind of hydrogenation catalyst and its application - Google Patents
A kind of hydrogenation catalyst and its application Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and its application, the catalyst contains carrier and at least one is selected from group VIII and at least one metal component selected from vib, it is characterized in that, the carrier is a kind of aluminum oxide article shaped containing amphoteric surfactant, on the basis of the carrier, the mass fraction of the amphoteric surfactant is 0.1% 10%.Compared with prior art, the performance of present invention offer catalyst is improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and its application.
Background technology
The environmental consciousness and increasingly stricter environmental regulation increasingly strengthened forces oil refining circle more to focus on clean fuel life
Technological development is produced, how the production super-low sulfur oil product of economical rationality turns into needs weight in oil refining circle's current and expected future regular period
One of problem that point solves.And it is then to produce clear gusoline most to develop the novel hydrogenation catalyst with more high activity and selectivity
One of economic method.
The content of the invention
The hydrogenation catalyst improved the technical problem to be solved in the present invention is to provide a kind of performance and its application.
The present invention relates to herein below：
1. a kind of hydrogenation catalyst, vib is selected from at least one containing carrier and at least one group VIII that is selected from
Metal component, it is characterised in that the carrier is a kind of aluminum oxide article shaped, contains both sexes table in the aluminum oxide article shaped
Face activating agent, on the basis of the carrier, the mass fraction of the amphoteric surfactant is 0.1%-10%.
2. the catalyst according to 1, it is characterised in that on the basis of the carrier, the amphoteric surfactant
Mass fraction is 0.3%-5%.
3. the catalyst according to 1, it is characterised in that the amphoteric surfactant is selected from amino acid type amphoteric surface
Activating agent, betaine type amphoteric surfac-tant, imidazoline type amphoteric surfactant, amine oxide type amphoteric surfactant and
One or more in silicon-contained type amphoteric surfactant.
4. the catalyst according to 3, it is characterised in that the amphoteric surfactant is selected from lauryl amino propionic acid
Sodium, lauryl amino propionic acid ammonium, Empigen sodium, Empigen ammonium, lauryl dihydroxyethyl
Glycine betaine sodium, lauryldihydroxyethyl betaine ammonium, cocoyl Sodium Glycinate, cocoyl glycine ammonium, N, N- dimethyl 12
Alkyl betaine, N, N- dimethyl-N -s [3- (trimethoxy silicon) propyl group] chlorination octadecyl ammonium (TPOAC), N, N- dimethyl-N -s
[3- (trimethoxy silicon) propyl group] tetradecyl chloride base ammonium (TPTAC), octadecyl dihydroxy ethyl amine oxide, myristyl dihydroxy second
Base amine oxide, stearamide propyl group amine oxide, cocamidopropyl propyl amide amine oxide, dodecanamide propyl amine oxide.
5. the catalyst 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 carrier, the adjuvant component
Mass fraction is less than 10%.
6. the article shaped according to 5, it is characterised in that on the basis of the carrier, the quality point of the adjuvant component
Number is 0.3%-5%.
7. according to the catalyst described in 1 or 5, it is characterised in that contain clay and/or molecular sieve in the article shaped, with
On the basis of the carrier, the mass fraction of the clay and/or molecular sieve is less than 35%.
8. the catalyst according to 7, it is characterised in that on the basis of the carrier, the clay and/or molecular sieve
Mass fraction is 1%-20%.
9. the catalyst according to 1, it is characterised in that on the basis of the catalyst, the catalyst contains 50-90
Weight % carrier, 1-10 weight % metal component of group VIII, 5-40 weight % metal component of group VIB.
10. the catalyst according to 9, it is characterised in that on the basis of the catalyst, the catalyst contains 60-
85 weight % carrier, 1.5-6 weight % metal component of group VIII, 10-35 weight % metal component of group VIB.
11. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, by hydrocarbon ils and catalyst haptoreaction, it is special
Sign is that the catalyst is the catalyst described in claim 1-10 any one.
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 through shaping by one or more of mixtures in hibbsite, monohydrate alumina and amorphous hydroted alumina
And it is made after being calcined.
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, with matter
The solid content of gauge is 5%-70%, wherein, the product of roasting and the boehmite in terms of butt or false boehmite
Mass ratio 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.Further
It is preferred that the 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 institute
State step（3）Hydrothermal conditions include：Temperature is 80-120 DEG C, 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, the amphoteric surfactant refers to the surfactant with two kinds of ionic natures of yin, yang,
It may be selected from amino acid type amphoteric surfactant, betaine type amphoteric surfac-tant, imidazoline type amphoteric surfactant, oxygen
Change amine type amphoteric surfactant and silicon-contained type amphoteric surfactant etc..Wherein, the example of amino acid type amphoteric surfactant
Son such as lauryl amino propionic acid sodium（Or ammonium）, cocoyl Sodium Glycinate（Or ammonium）；The example of betaine type amphoteric surfac-tant
Such as Empigen（Sodium salt or ammonium salt）, lauryldihydroxyethyl betaine（Sodium salt or ammonium salt）, N, N- dimethyl
Empgen BB etc.；Imidazoline type amphoteric surfactant example such as 2- undecyls-N- acetates-N-（2- ethoxys）
Imidazoline, 2- undecyls-N-（2- ethoxys）-N-（2 '-hydroxypropyl sulfo group）Imidazoline etc.；Amine oxide type amophoteric surface active
Agent example such as octadecyl dihydroxy ethyl amine oxide, myristyl dihydroxy ethyl amine oxide, stearamide propyl group amine oxide, cocounut oil
LAO, dodecanamide propyl amine oxide etc.；And N, N- dimethyl-N-[3- (trimethoxy silicon) propyl group] chlorination ten
The silicon-contained type such as eight alkylammoniums (TPOAC), N, N- dimethyl-N -s [3- (trimethoxy silicon) propyl group] tetradecyl chloride base ammonium (TPTAC)
Amphoteric surfactant.
It is being enough to make the premise for containing 0.1%-10%, preferably 0.3%-5% amphoteric surfactant in the article shaped
Under, the present invention is not limited the method that amphoteric surfactant is introduced in the aluminum oxide article shaped.
In one preferred embodiment, the method that amphoteric surfactant is introduced in the aluminum oxide article shaped,
Including：（1）Impregnate the aluminum oxide article shaped with the solution containing amphoteric surfactant, the volume of the maceration extract with it is described into
The ratio between pore volume of type thing is 0.5-20, preferably 1-15；（2）The mixture that dipping obtains is subjected to heat in closed reactor
Processing, heat treatment temperature be room temperature to 250 DEG C, preferably 60 DEG C to 220 DEG C, the time be -48 hours 0.5 hour, preferably 1 is small
When -36 hours；（3）Drying steps（2）Product, the drying condition includes：Temperature be 40 DEG C -250 DEG C, preferably 100 DEG C -
180 DEG C, the time is -24 hours 1 hour, preferably -18 hours 2 hours.
Wherein, the room temperature can be the indoor temperature in interior each season throughout the year, generally 5-40 DEG C.The dipping
The solvent of liquid can be the various solvents that can dissolve the amphoteric surfactant, preferably water, ammoniacal liquor, ethanol.
On the premise of being enough to make the content satisfaction requirement of amphoteric surfactant in the final article shaped, the present invention is right
The content and dipping time of amphoteric surfactant in maceration extract are not particularly limited.In specific implementation, preferably control
Step（1）Described in amphoteric surfactant in maceration extract and the weight ratio of aluminum oxide article shaped be 0.01-10：100, enter
One step is 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, it is introduced into the aluminum oxide article shaped in the method for amphoteric surfactant, step（3）Dry
Purpose is in the solvent in impregnation product is removed, on the premise of being enough to realize the purpose, method of the present invention to the drying
Do not limit, 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, on the basis of the carrier, the mass fraction of the adjuvant component is less than 10%,
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, it is described viscous on the basis of the carrier
The mass fraction of soil and/or molecular 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.
In the present invention, the hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or hydrocracking
Catalyst.The metal component selected from group VIII and selected from vib in the catalyst is conventional selection, for example, described
Metal component of group VIII is selected from cobalt and/or nickel, and metal component of group VIB is selected from molybdenum and/or tungsten.
In a specific embodiment, counted and on the basis of the catalyst by oxide, catalyst of the present invention is preferred
Carrier containing 50-90 weight %, 1-10 weight % metal component of group VIII, 5-40 weight % metal component of group VIB；
Further preferred catalyst contains 60-85 weight % carrier, 1.5-6 weight % metal component of group VIII, 10-35 weight %
Metal component of group VIB.
In the present invention, at least one group VIII and at least one vib metals component are introduced into the carrier
Method is method customary in the art, for example, it may be will contain at least one group VIII and at least one selected from vib gold
The method that category compound is configured to impregnate after mixed solution the carrier；Can be by containing at least one group VIII and at least
A kind of method for individually preparing impregnated carrier after solution selected from vib metals compound.Wherein, by metallic components
The regulation and control of the concentration of solution, dosage or carrier dosage, can prepare the catalyst of specified content, this is ability
Field technique personnel are readily appreciated by.
According to the present invention, after the impregnation steps are completed, it the step such as can optionally be dried, be calcined or not be calcined
Suddenly.The condition of the drying and roasting is conventional, for example, drying temperature is 100-300 DEG C, preferably 100-280 DEG C, is done
The dry time is 1-12 hours, preferably 2-8 hours；Sintering temperature is 350-550 DEG C, and preferably 400-500 DEG C, roasting time is
1-10 hours, preferably 2-8 hours.
One or more in the soluble compound of the group VIII metallic compound selected from these metals, for example,
Can be the one or more in the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
One or more in described soluble compound of the vib metals compound selected from these metals, for example,
Can be the one or more in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
According to catalyst provided by the invention, before the use preferably in presence of hydrogen, at a temperature of 140-370 DEG C
Carry out presulfurization with sulphur, hydrogen sulfide or containing sulfur feedstock, this presulfurization can be carried out outside device it is also In-situ sulphiding in device, by it
The active metal component loaded is converted into metal sulfide component.
In the present invention, to described hydrotreating reaction condition, there is no particular limitation, and preferable reaction condition includes：Instead
Answer 200-420 DEG C of temperature, more preferably 220-400 DEG C, 2-18 MPas of pressure, more preferably 2-15 MPas, during liquid
Air speed 0.3-10 hours- 1, more preferably 0.3-5 hours- 1, hydrogen to oil volume ratio 50-5000, more preferably 50-
4000。
The device of the hydrogenation reaction can be enough to make the feedstock oil urge with described under hydrogenation conditions any
Carried out in the catalytic reaction dress device of agent, for example, the reaction is in fixed bed reactors, moving-burden bed reactor or ebullated bed
Carried out in reactor.
All kinds of hydrocarbon oil crude materials can be processed using catalyst provided by the invention.For example, the hydrocarbon oil crude material can be each
Kind heavy mineral oil or artificial oil or their mixed fraction oil, such as selected from crude oil, distillate, solvent-refined oil, slack wax, wax
One or more in lower oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.
Compared with prior art, the hydrogenation activity of present invention offer catalyst is improved, particularly by containing amphoteric surface
Catalyst prepared by carrier prepared by the hydrated alumina that the use of activating agent is modified through method provided by the invention, this modification
It is particularly evident.
For example, prepared respectively with the aluminum oxide article shaped provided by the invention containing amphoteric surfactant and conventional method
Carrier prepares tenor 2.4%NiO and 12%MoO3 Hydrobon catalyst 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 hydrogenation of two kinds of catalyst is taken off
Sulphur activity is evaluated.Using catalyst DC activity as 100, catalyst C hydrodesulfurization activity is 111.As a result show, with showing
There is technology to provide catalyst prepared by carrier to compare, the hydrodesulfurization activity that catalyst is prepared by present invention offer carrier substantially carries
It is high.
Embodiment
The present invention will be further illustrated in following example, but not thereby limiting the invention.
In following examples, analysis measure is carried out to the content of each element in catalyst using x-ray fluorescence method
（RIPP132-90, referring to：Petrochemical Engineering Analysis method（RIPP test methods）, Yang Cui surely compile by grade, Science Press, and 1990,
371-375）.
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.
Modified boehmite and/or false boehmite used in embodiment 1-10 declaratives carriers, it is prepared
Method and the alumina support thus prepared.
The hydrated alumina used in experiment is：
CL-A powder（False boehmite powder）, it is 100% with respect to relative crystallinity, grain size 2.9nm, the weight of butt 70
% is measured, purchased from sinopec Chang Ling catalyst branch company.
CL-B powder（Boehmite）, it is 100%, grain size 5.2nm, the weight % of butt 78 with respect to relative crystallinity, purchases
From sinopec Chang Ling catalyst branch company）.
CL-C powder（Gibbsite（α-Al2O3·3H2O））, it is 100%, grain size 156nm with respect to relative crystallinity, does
The weight % of base 65, 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 outer
Connect the cloverleaf pattern bar that circular diameter is 1.6 millimeters.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 crystal grain are characterized by X-ray diffraction method
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.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-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.Measure is adsorbed/is desorbed by N2
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.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-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-450 in terms of butt are weighed respectively
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
Gram, 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, 8 grams of CL-C-600 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）, by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are 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 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, obtained through changing
The hydrated alumina Q-S7 of property.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, as a result arranged
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 outer
Connect the cloverleaf pattern bar that circular diameter is 1.6 millimeters.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 crystal grain are characterized by X-ray diffraction method
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
Gram, 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, 8 grams of CL-C-600 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）, by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are 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 is heated to after closed 4 hours.After being down to room temperature, high pressure kettle cover is opened, adds 11.75 grams of ammonium dihydrogen phosphates,
Room temperature continues stirring 24 hours, after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the modified oxygen containing auxiliary agent phosphorus
Change aluminium hydrate Q-S8.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, are as a result listed in table 1
In.
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 outer
Connect the cloverleaf pattern bar that circular diameter is 1.6 millimeters.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 crystal grain are characterized by X-ray diffraction method
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.It is glimmering using X
Light method determines the content of adjuvant component, and 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.
What embodiment 11-13 illustrated that the present invention uses prepare boehmite by conventional method of modifying and/or a false water is soft
The modifier of aluminium stone and the alumina support being prepared by the modifier.
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 the aluminum oxide article shaped provided by the invention containing amphoteric surfactant and its preparation side
Method.
Embodiment 14
1200 grams of carrier S is weighed to be placed in autoclave；1.28 grams of lauryl amino propionic acid ammoniums are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 90 DEG C of constant temperature 24 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S1 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 15
2200 grams of carrier S is weighed to be placed in autoclave；1.58 grams of cocoyl Sodium Glycinates are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after placement 48 hours at room temperature into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S2 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 16
3200 grams of carrier S is weighed to be placed in autoclave；3.62 grams of lauryl amino propionic acid ammoniums are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 6 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 60 DEG C of constant temperature 18 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S3 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 17
4200 grams of carrier S is weighed to be placed in autoclave；1.05 grams of lauryl amino propionic acid sodium are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 3 milliliters of concentrated ammonia liquors of mass fraction 25%, 140 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 120 DEG C of constant temperature 6 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S4 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 18
5200 grams of carrier S is weighed to be placed in autoclave；0.82 gram of cocoyl Sodium Glycinate is dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 2.5 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, Ran Houjia
Enter into autoclave, it is closed after 160 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S5 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 19
6200 grams of carrier S is weighed to be placed in autoclave；By 4.49 grams of N, N- dimethyl-N -s [3- (trimethoxy silicon) propyl group] chlorine
Change octadecyl ammonium and be dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By 1 milliliter of concentrated ammonia liquor of mass fraction 25%, 150 milliliters of anhydrous second
Alcohol, surplus are water, are mixed）, it is then added in autoclave, it is closed after 180 DEG C of constant temperature 2 hours.By sample after cooling
Dried 4 hours in 120 DEG C, obtain the aluminum oxide article shaped R-S6 containing amphoteric surfactant.Amophoteric surface active in carrier
The mass fraction of agent is listed in table 3.
Embodiment 20
7200 grams of carrier S is weighed to be placed in autoclave；5.11 grams of cocoyl glycine ammoniums are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 5 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 110 DEG C of constant temperature 4 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S7 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 21
8200 grams of carrier S is weighed to be placed in autoclave；4.26 grams of lauryl amino propionic acid ammoniums are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 3 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 120 DEG C of constant temperature 4 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S8 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 22
9200 grams of carrier S is weighed to be placed in autoclave；4.69 grams of lauryl amino propionic acid ammoniums are dissolved in ammoniacal liquor-ethanol solution
200 milliliters（By 3 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, then add
It is closed after 130 DEG C of constant temperature 4 hours into autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes table
The aluminum oxide article shaped R-S9 of face activating agent.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 23
10200 grams of carrier S is weighed to be placed in autoclave；It is molten that 1.06 grams of lauryl amino propionic acid ammoniums are dissolved in ammonia water-ethanol
200 milliliters of liquid（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, Ran Houjia
Enter into autoclave, it is closed after 80 DEG C of constant temperature 10 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S10 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 24
11200 grams of carrier S is weighed to be placed in autoclave；It is molten that 1.28 grams of lauryl amino propionic acid ammoniums are dissolved in ammonia water-ethanol
200 milliliters of liquid（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, Ran Houjia
Enter into autoclave, it is closed after 90 DEG C of constant temperature 24 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S11 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 25
12200 grams of carrier S is weighed to be placed in autoclave；It is molten that 1.28 grams of lauryl amino propionic acid ammoniums are dissolved in ammonia water-ethanol
200 milliliters of liquid（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, Ran Houjia
Enter into autoclave, it is closed after 90 DEG C of constant temperature 24 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S12 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 26
13200 grams of carrier S is weighed to be placed in autoclave；It is molten that 1.28 grams of lauryl amino propionic acid ammoniums are dissolved in ammonia water-ethanol
200 milliliters of liquid（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, Ran Houjia
Enter into autoclave, it is closed after 90 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing both sexes
The aluminum oxide article shaped R-S13 of surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 27
Weigh support C L-A-Al2O3200 grams are placed in autoclave；By 1.28 grams of lauryl amino propionic acid ammoniums be dissolved in ammoniacal liquor-
200 milliliters of ethanol solution（By 2 milliliters of concentrated ammonia liquors of mass fraction 25%, 130 milliliters of absolute ethyl alcohols, surplus is water, is mixed）,
It is then added in autoclave, it is closed after 90 DEG C of constant temperature 24 hours.Sample is dried 4 hours in 120 DEG C after cooling, contained
There is the aluminum oxide article shaped R-S14 of amphoteric surfactant.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
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.
14200 grams of carrier S is weighed to be placed in autoclave;By 5.35 grams of N, N- dimethyl-N -s [3- (trimethoxy silicon) propyl group]
Tetradecyl chloride base ammonium and 0.93 gram of cocoyl Sodium Glycinate are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By 3 milliliters of mass fractions
25% concentrated ammonia liquor, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added in autoclave, it is closed after 100 DEG C
Constant temperature 2 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains the aluminum oxide article shaped R- containing amphoteric surfactant
S15.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
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；By 6.76 grams of lauryl amino propionic acid ammoniums, 1.15 grams of myristyls
Dihydroxy ethyl amine oxide and 0.68 gram of cocoyl Sodium Glycinate are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By 2 milliliters of mass fractions
25% concentrated ammonia liquor, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added in autoclave, it is closed after 100 DEG C
Constant temperature 3 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains the aluminum oxide article shaped R- containing amphoteric surfactant
S16.The mass fraction of amphoteric surfactant is listed in table 3 in carrier.
Embodiment 30-45 illustrates catalyst provided by the invention and its preparation.
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, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8, R-S9, R-S10, R-S11, R- that example 14~29 is prepared
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
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 (11)
1. a kind of hydrogenation catalyst, containing carrier and at least one group VIII and at least one gold selected from vib are selected from
Belong to component, it is characterised in that the carrier is a kind of aluminum oxide article shaped, is lived in the aluminum oxide article shaped containing amphoteric surface
Property agent, on the basis of the carrier, the mass fraction of the amphoteric surfactant is 0.1%-10%；
The aluminum oxide article shaped obtains for a kind of boehmite of modification and/or false boehmite after being molded, being calcined
Gama-alumina；
The method of the modified boehmite and/or false boehmite includes：（1）At least one hydrated alumina is roasted
Burn, 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）Obtain
Product of roasting mixes with least one boehmite and/or false boehmite and water, obtains a kind of mixture；（3）Will
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, obtain modified boehmite and/or
False boehmite.
2. catalyst according to claim 1, it is characterised in that on the basis of the carrier, the amophoteric surface active
The mass fraction of agent is 0.3%-5%.
3. catalyst according to claim 1, it is characterised in that the amphoteric surfactant is selected from amino acid type amphoteric
Surfactant, betaine type amphoteric surfac-tant, imidazoline type amphoteric surfactant, amine oxide type amophoteric surface active
One or more in agent and silicon-contained type amphoteric surfactant.
4. catalyst according to claim 3, it is characterised in that the amphoteric surfactant is selected from lauryl amino third
Sour sodium, lauryl amino propionic acid ammonium, Empigen sodium, Empigen ammonium, lauryl dihydroxy second
Base glycine betaine sodium, lauryldihydroxyethyl betaine ammonium, cocoyl Sodium Glycinate, cocoyl glycine ammonium, N, N- dimethyl ten
Dialkyl group glycine betaine, N, N- dimethyl-N -s [3- (trimethoxy silicon) propyl group] chlorination octadecyl ammonium (TPOAC), N, N- diformazans
Base-N- [3- (trimethoxy silicon) propyl group] tetradecyl chloride base ammonium (TPTAC), octadecyl dihydroxy ethyl amine oxide, myristyl
Dihydroxy ethyl amine oxide, stearamide propyl group amine oxide, cocamidopropyl propyl amide amine oxide, dodecanamide propyl amine oxide.
5. catalyst according to claim 1, it is characterised in that in the aluminum oxide article shaped contain selected from silica,
One or more of adjuvant components in titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, on the basis of the carrier, institute
The mass fraction for stating adjuvant component is less than 10%.
6. catalyst according to claim 5, it is characterised in that on the basis of the carrier, the matter of the adjuvant component
Amount fraction is 0.3%-5%.
7. catalyst according to claim 1 or 5, it is characterised in that in the aluminum oxide article shaped containing clay and/or
Molecular sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is less than 35%.
8. catalyst according to claim 7, it is characterised in that on the basis of the carrier, the clay and/or molecule
The mass fraction of sieve is 1%-20%.
9. catalyst according to claim 1, it is characterised in that on the basis of the catalyst, the catalyst contains
50-90 weight % carrier, 1-10 weight % metal component of group VIII, 5-40 weight % metal component of group VIB.
10. catalyst according to claim 9, it is characterised in that on the basis of the catalyst, the catalyst contains
60-85 weight % carrier, 1.5-6 weight % metal component of group VIII, 10-35 weight % metal component of group VIB.
11. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, by hydrocarbon ils and catalyst haptoreaction, its feature exists
In the catalyst is the catalyst described in claim 1-10 any one.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368939A (en) * | 1999-08-11 | 2002-09-11 | 阿克佐诺贝尔公司 | Process for preparation of quasi-crystalline boehmites from inexpensive precursors |
| CN1415705A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for producing good quality diesel oil |
| CN1626625A (en) * | 2003-12-10 | 2005-06-15 | 中国石油化工股份有限公司 | Demetallization catalyst of addig hydrogen to residual oil and preparation method |
| CN101462079A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| CN102161002A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Catalyst for hydrotreatment and application thereof |
| CN103041869A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of spherical catalyst carrier |
| CN103374393A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Hydrotreatment method for hydrocarbon oil |
-
2014
- 2014-04-09 CN CN201410140384.7A patent/CN104971732B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368939A (en) * | 1999-08-11 | 2002-09-11 | 阿克佐诺贝尔公司 | Process for preparation of quasi-crystalline boehmites from inexpensive precursors |
| CN1415705A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for producing good quality diesel oil |
| CN1626625A (en) * | 2003-12-10 | 2005-06-15 | 中国石油化工股份有限公司 | Demetallization catalyst of addig hydrogen to residual oil and preparation method |
| CN101462079A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| CN102161002A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Catalyst for hydrotreatment and application thereof |
| CN103041869A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of spherical catalyst carrier |
| CN103374393A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Hydrotreatment method for hydrocarbon oil |
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