CN104971779B - A kind of hydrogenation catalyst and its application - Google Patents
A kind of hydrogenation catalyst and its application Download PDFInfo
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- CN104971779B CN104971779B CN201410140401.7A CN201410140401A CN104971779B CN 104971779 B CN104971779 B CN 104971779B CN 201410140401 A CN201410140401 A CN 201410140401A CN 104971779 B CN104971779 B CN 104971779B
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Abstract
A kind of hydrogenation catalyst and its application, the catalyst contains carrier and at least one 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 anionic surfactant, on the basis of the carrier, the mass fraction of the anionic 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
Increasingly enhanced environmental consciousness and increasingly stricter environmental regulation force 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 is solved.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 containing carrier and at least one group VIII and at least one of being selected from
Metal component, it is characterised in that the carrier is a kind of aluminum oxide article shaped, contains anion in the aluminum oxide article shaped
Surfactant, on the basis of the carrier, the mass fraction of the anion surfactant is 0.1%-10%.
2. the catalyst according to 1, it is characterised in that on the basis of the carrier, the anionic surface activity
The mass fraction of agent is 0.3%-5%.
3. the catalyst according to 1, it is characterised in that the anionic surfactant is selected from carboxylate, sulfuric acid
One or more in ester salt, sulfonate and phosphate ester salt.
4. the catalyst according to 3, it is characterised in that the anionic surfactant is selected from ammonium oleate, oleic acid
One or more in sodium, ammonium stearate, odium stearate, neopelex.
5. the catalyst according to 1, it is characterised in that contain in the aluminum oxide article shaped selected from silica, oxidation
One or more of adjuvant components in titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide, it is described to help on the basis of the carrier
The mass fraction of agent component 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. the catalyst according to 1 or 5, it is characterised in that contain clay and/or molecule in the aluminum oxide article shaped
Sieve, 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
Levy and be, the catalyst is the catalyst described in claim 1-10 any one.
In the present invention, one or more of the aluminum oxide in γ, η, θ, δ and χ, preferably gama-alumina.Institute
Stating aluminum oxide has ratio surface and the pore volume of conventional alumina, and the ratio surface of preferential oxidation aluminium is 150-350 meters2/ gram, enter
One step is preferably 180-320 meters2/ gram, preferably the pore volume of aluminum oxide is 0.4-1.1 mls/g, more preferably 0.5-0.9
Ml/g.They can be that commercially available commodity can also be prepared by any one method in the prior art.For example, it may be by selecting
From one or more of mixtures in hibbsite, monohydrate alumina and amorphous hydroted alumina through being molded and being calcined
After be made.
The article shaped of the aluminum oxide is prepared using customary way, such as tabletting, spin, extrusion method.Adopting
When being molded with customary way, to ensure that what is be molded is smoothed out to foregoing material to be formed（For example, hibbsite,
One or more of mixtures in monohydrate alumina and amorphous hydroted alumina）It is middle introducing auxiliary agent be allowed, for example when
During extrusion, appropriate extrusion aid and water can be introduced into foregoing material to be formed, extrusion molding afterwards.The kind of the extrusion aid
Class and consumption may each be that this area is conventional, such as common extrusion aid can selected from sesbania powder, methylcellulose, starch,
One or more in polyvinyl 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 is obtained after shaping, roasting.
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 is mixed 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 step preferably（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.
It is preferred that the step（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.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 step preferably（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, with X-ray diffraction characterize, be one kind at 14.5 ° ± 0.5 °（2
θ）There is wide and disperse（020）The hydrated alumina of crystallographic plane diffraction peak.
The boehmite is also known as boehmite, with X-ray diffraction characterize, be one kind 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
The relative crystallinity raising of processing 4-24 hours, thus modified obtained boehmite and/or false boehmite, 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 step for preferably making the crystalline phase of the modified product consistent with initiation material
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
It is preferred that the 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 be passed through under inert gas conditions carry out.When the roasting is passed through inert gas, the inert gas can
To be the arbitrary not oxygen-containing gas for being 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 weight of product and the oxidation before roasting after roasting
The percentage of the weight ratio of aluminium hydrate, the weight of the preceding hydrated alumina of weight ÷ roastings of product 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 anion surfactant is that can generate hydrophobicity anion chemical combination after a class is dissociated in water
Thing.For example, the one or more in carboxylate, sulfuric acid, sulfonate and phosphate ester salt.Carboxylate preferably wherein, for example,
Ammonium oleate, enuatrol, ammonium stearate, odium stearate, neopelex etc..
It is being enough to make to contain 0.1%-10% in the article shaped, preferably before 0.3%-5% anion surfactant
Put, the present invention is not limited the method that anion surfactant is introduced in the aluminum oxide article shaped.
In one preferred embodiment, the side of anionic surfactant is introduced in the aluminum oxide article shaped
Method, including：（1）The aluminum oxide article shaped, the volume of the maceration extract are impregnated with the solution containing anionic surfactant
It is 0.5-20, preferably 1-15 with the ratio between the pore volume of the article shaped；（2）Obtained mixture will be impregnated in closed reactor
It is middle to be heat-treated, 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 -36 hours 1 hour；（3）Drying steps（2）Product, the drying condition includes：Temperature is 40 DEG C -250 DEG C, excellent
Elect 100 DEG C -180 DEG C as, the time is -24 hours 1 hour, preferably -18 hours 2 hours.
Wherein, the room temperature can be the indoor temperature in each interior season throughout the year, generally 5-40 DEG C.The dipping
The solvent of liquid can be that can dissolve the various solvents of the anion surfactant, preferably water, ammoniacal liquor, ethanol.
On the premise of being enough to make the content satisfaction requirement of anion surfactant in the final article shaped, the present invention
Content and dipping time to the anion surfactant in maceration extract are not particularly limited.In specific implementation, preferably
Rate-determining steps（1）Described in anion surfactant in maceration extract with the weight ratio of aluminum oxide article shaped be 0.01-
10：100, 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, it is introduced into the aluminum oxide article shaped in the method for anion surfactant, step（3）Dry
Purpose be to remove the solvent in impregnation product, on the premise of being enough to realize the purpose, the present invention is to the side of the drying
Method is not limited, for example, can be the method or vacuum drying method of heat drying.
It can contain in the present invention, in the aluminum oxide article shaped and be selected from silica, titanium oxide, magnesia, zirconium oxide, oxygen
Change one or more of adjuvant components in thorium, beryllium oxide, 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 containing 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 the introducing adjuvant component is 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 hibbsite, monohydrate alumina and the 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 of the 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 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 for 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 be with commercially available, it would however also be possible to employ prepared by conventional method.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 be containing at least one group VIII and at least one selected from vib gold
The method that category compound is configured to impregnate the carrier after mixed solution；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, consumption or carrier consumption, 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.
The catalyst provided according to the present 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 reaction condition preferably 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.
The catalyst provided using the present invention can process all kinds of hydrocarbon oil crude materials.For example, the hydrocarbon oil crude material can be each
Heavy mineral oil or artificial oil or their mixed fraction oil are planted, 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 table containing anion
Catalyst prepared by carrier prepared by the hydrated alumina that the method that the use of face activating agent is provided through the present invention is modified, it is this to change
Property is particularly evident.
For example, prepared by the aluminum oxide article shaped containing anion surfactant and conventional method that are provided respectively with the present invention
Carrier prepare tenor 2.4%NiO and 12%MoO3Hydrobon catalyst C and DC（Reference agent）.With containing 4,6- diformazans
Base dibenzothiophenes（4,6-DMDBT）The mixed solution of 0.59 weight % n-decane is raw material, to the hydrogenation of two kinds of catalyst
It is desulphurizing activated to be evaluated.Using catalyst DC activity as 100, catalyst C hydrodesulfurization activity is 111.As a result show, with
The catalyst that prior art provides carrier preparation is compared, and the hydrodesulfurization activity for preparing catalyst by present invention offer carrier is obvious
Improve.
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
Wei Qiao, Sun Gui are big to be compiled, Sinopec publishing house, 2000,57-89）With《Petrochemical Engineering Analysis method（RIPP test methods）》（Poplar
Kingfisher is fixed, Gu Kanying, and Wu Wenhui is compiled, Science Press, 1990,394-405）In X-ray diffraction method carry out.
Modified boehmite used in embodiment 1-10 declaratives carriers and/or false boehmite, 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%, grain size 2.9nm, the weight of butt 70 with respect to relative crystallinity
% 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, purchase with respect to relative crystallinity
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, banded extruder is used（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.After wet bar is dried 4 hours through 120 DEG C, 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, banded extruder is used（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.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere
Under in Muffle furnace 600 DEG C of constant temperature 4 hours, obtain alumina support CL-B-Al2O3.It is characterized by X-ray diffraction method brilliant
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 and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred into band to stir
The volume mixed in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C, and constant temperature 4 under agitation
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified product Q-S1 is obtained.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.After wet bar is dried 4 hours through 120 DEG C, 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.Its specific surface area of measure and pore volume are adsorbed/are desorbed by N2, 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 and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S2 is obtained.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（Be the same as Example 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 is determined
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 and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S3 is obtained.Pass through X-ray
Diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
Formed alumina and its preparation that the present invention is provided：
By Q-S3 banded extruders（Be the same as Example 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 is determined
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 and 3600 grams of deionized waters are mixed into slurries；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 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 characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S4 banded extruders（Be the same as Example 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 is determined
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 and 3100 grams of deionized waters are mixed into slurries；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 60 DEG C of constant temperature 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 characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S5 banded extruders（Be the same as Example 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 is determined
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 and 3200 grams of deionized waters are mixed into slurries；It is 5 liters that the slurries are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 100 DEG C of constant temperature 24 hours；Room temperature and after filtering is down to,
Filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S6 is obtained.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（Be the same as Example 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.Measure is adsorbed/is desorbed by N2
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 autoclave of the volume with stirring for 5 liters 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, 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.After wet bar is dried 4 hours through 120 DEG C, 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.Its specific surface area of measure and pore volume are adsorbed/are desorbed by N2, 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 autoclave of the volume with stirring for 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 11.75 grams of ammonium dihydrogen phosphates,
Room temperature continues to stir 24 hours, after filtering, filter cake is dried 8 hours in 120 DEG C, the modified oxygen containing auxiliary agent phosphorus is obtained
Change aluminium hydrate Q-S8.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, table 1 is as a result listed in
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.After wet bar is dried 4 hours through 120 DEG C, 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.Its specific surface area of measure and pore volume are adsorbed/are desorbed by N2, 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 and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues to stir 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 characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S9 banded extruders（Be the same as Example 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.Measure is adsorbed/is desorbed by N2
Its specific surface area and pore volume, the results are shown in Table 2.The content of adjuvant component, the titanium in terms of element are determined using X-fluorescence method
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 and 3600 grams of deionized waters are mixed into slurries；The slurries are transferred into band to stir
The volume mixed in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 200 DEG C, and constant temperature 4 under agitation
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified product Q-S10 is obtained.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.After wet bar is dried 4 hours through 120 DEG C, 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.Its specific surface area of measure and pore volume are adsorbed/are desorbed by N2, the results are shown in Table 2.
Embodiment 11-13 illustrate the present invention use boehmite is prepared by conventional method of modifying and/or a false water is soft
The modifier of aluminium stone and the alumina support prepared by the modifier.
Embodiment 11
470 grams of the CL-A powder in terms of butt is weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
The volume with stirring is transferred to in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-1 is obtained.
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（Be the same as Example 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, it is mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to
Volume with stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；Drop
To room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-2 is obtained.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（Be the same as Example 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, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
The volume with stirring is transferred to in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 200 DEG C of constant temperature 4
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-3 is obtained.
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（Be the same as Example 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.Survey is adsorbed/is desorbed by N2
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；Determining the knot of 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 illustrate the carrier of offer of the present invention, the i.e. aluminum oxide containing anionic surfactant into
Type thing and preparation method thereof.
Embodiment 14
1200 grams of carrier S is weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-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, obtained containing anionic surface activity
The aluminum oxide article shaped R-S1 of agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 15
2200 grams of carrier S is weighed to be placed in autoclave；1.66 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-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 to be placed 48 hours after room temperature.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface activity
The aluminum oxide article shaped R-S2 of agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 16
3200 grams of carrier S is weighed to be placed in autoclave；3.58 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
6 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 60 DEG C of constant temperature 18 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface activity
The aluminum oxide article shaped R-S3 of agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 17
4200 grams of carrier S is weighed to be placed in autoclave；1.08 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
3 milliliters of concentrated ammonia liquors of mass fraction 25%, 140 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added in autoclave,
It is closed after 120 DEG C of constant temperature 6 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface activity
The aluminum oxide article shaped R-S4 of agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 18
5200 grams of carrier S is weighed to be placed in autoclave；0.77 gram of ammonium oleate is dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
2.5 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to autoclave
In, it is closed after 160 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains living containing anionic surface
The aluminum oxide article shaped R-S5 of property agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 19
6200 grams of carrier S is weighed to be placed in autoclave；4.55 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
8 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added in autoclave,
It is closed after 180 DEG C of constant temperature 2 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface activity
The aluminum oxide article shaped R-S6 of agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 20
7200 grams of carrier S is weighed to be placed in autoclave；4.93 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to autoclave
In, it is closed after 110 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains living containing anionic surface
The aluminum oxide article shaped R-S7 of property agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 21
8200 grams of carrier S is weighed to be placed in autoclave；4.31 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to autoclave
In, it is closed after 120 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains living containing anionic surface
The aluminum oxide article shaped R-S8 of property agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 22
9200 grams of carrier S is weighed to be placed in autoclave；4.46 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By
12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to autoclave
In, it is closed after 130 DEG C of constant temperature 4 hours.Sample is dried 4 hours in 120 DEG C after cooling, obtains living containing anionic surface
The aluminum oxide article shaped R-S9 of property agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 23
10200 grams of carrier S is weighed to be placed in autoclave；1.05 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution
（By 12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to high pressure
It is closed after 80 DEG C of constant temperature 10 hours in kettle.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface
The aluminum oxide article shaped R-S10 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 24
11200 grams of carrier S is weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution
（By 12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to high pressure
It is closed after 90 DEG C of constant temperature 24 hours in kettle.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface
The aluminum oxide article shaped R-S11 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 25
12200 grams of carrier S is weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution
（By 12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to high pressure
It is closed after 90 DEG C of constant temperature 24 hours in kettle.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface
The aluminum oxide article shaped R-S12 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 26
13200 grams of carrier S is weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammoniacal liquor-ethanol solution
（By 12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to high pressure
It is closed after 90 DEG C of constant temperature 4 hours in kettle.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic surface
The aluminum oxide article shaped R-S13 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 27
Weigh support C L-A-Al2O3200 grams are placed in autoclave；1.25 grams of ammonium oleates are dissolved in ammoniacal liquor-ethanol solution 200
Milliliter（By 12 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed）, it is then added to
It is closed after 90 DEG C of constant temperature 24 hours in autoclave.Sample is dried 4 hours in 120 DEG C after cooling, obtained containing anionic
The aluminum oxide article shaped R-S14 of surfactant.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 28
The modified aluminas hydrate Q-S2 powder with the equivalent of embodiment 2 is prepared, then with 25 grams of silicon dioxide powders（In being purchased from
Petrochemical industry 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 extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, it is dry 4 hours through 120 DEG C, in air atmosphere finally
600 DEG C are raised to 4 DEG C/min of heating rate in Muffle furnace, then in 600 DEG C of constant temperature 4 hours, alumina support S14 is obtained.
14200 grams of carrier S is weighed to be placed in autoclave, 5.25 grams of ammonium oleates and 0.89 gram of neopelex are molten
In 200 milliliters of ammoniacal liquor-ethanol solution（By 13 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of absolute ethyl alcohols, surplus is water, is mixed
Conjunction is formed）, it is then added in autoclave, it is closed after 100 DEG C of constant temperature 2 hours.It is after cooling that sample is small in 120 DEG C of dryings 4
When, obtain the aluminum oxide article shaped R-S15 containing anionic surfactant.The matter of anionic surfactant in carrier
Amount fraction is listed in table 3.
Embodiment 29
The hydrated alumina Q-S2 powder with the modification of the equivalent of embodiment 2 is prepared, then with 36 grams of Hydrogen Y molecular sieve powder
（Na2O content 0.2%, cell parameter 2.464, relative crystallinity 88%, purchased from sinopec Chang Ling catalyst branch company）Used after mixing
Banded extruder（Manufacturer：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26(Ⅲ)）It is 1.6 millis to be extruded into circumscribed circle diameter
The cloverleaf pattern bar of rice, is dried 4 hours through 120 DEG C, finally in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate
600 DEG C are raised to, 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 6.68 grams of ammonium oleates, 1.23 grams of neopelexes and
0.66 gram of enuatrol is dissolved in 200 milliliters of ammoniacal liquor-ethanol solution（By 15 milliliters of concentrated ammonia liquors of mass fraction 25%, 150 milliliters of anhydrous second
Alcohol, surplus is water, is mixed）, it is then added in autoclave, it is closed after 100 DEG C of constant temperature 3 hours.By sample after cooling
Dried 4 hours in 120 DEG C, obtain the aluminum oxide article shaped R-S16 containing anionic surfactant.Anionic in carrier
The mass fraction of surfactant is listed in table 3.
Embodiment 30-45 illustrates the catalyst of the invention provided 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
L-A-Al2O3200 grams of support C is weighed, 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, by catalyst breakage into the particle of 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 for 280 DEG C, raw material is cut.Reaction condition includes：Raw material feed rate is 0.2
Ml/min, pressure is 4.14MPa, and hydrogen to oil volume ratio is 900.Reaction is sampled 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, the desulfurization degree that X is 4,6-DMDBT（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/AD1A in) × 100%, 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, contain anionic surface in the aluminum oxide article shaped
Activating agent, on the basis of the carrier, the mass fraction of the anion surfactant is 0.1%-10%；In the aluminum oxide
The method that anionic surfactant is introduced in article shaped, including：（1）Impregnated with the solution containing anionic surfactant
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 be heat-treated in closed reactor, heat treatment temperature be room temperature to 250 DEG C, the time is 0.5 hour -48 small
When；（3）Drying steps（2）Product, the drying condition includes：Temperature is 40 DEG C -250 DEG C, and the time is -24 hours 1 hour.
2. catalyst according to claim 1, it is characterised in that on the basis of the carrier, the anionic surface
The mass fraction of activating agent is 0.3%-5%.
3. catalyst according to claim 1, it is characterised in that the anionic surfactant be selected from carboxylate,
One or more in sulfuric acid, sulfonate and phosphate ester salt.
4. catalyst according to claim 3, it is characterised in that the anionic surfactant be selected from ammonium oleate,
One or more in enuatrol, ammonium stearate, odium stearate, neopelex.
5. catalyst according to claim 1, it is characterised in that contain in the aluminum oxide article shaped 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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