CN106140309B - A kind of hydrogenation catalyst and preparation method and applications - Google Patents
A kind of hydrogenation catalyst and preparation method and applications Download PDFInfo
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- CN106140309B CN106140309B CN201510145499.XA CN201510145499A CN106140309B CN 106140309 B CN106140309 B CN 106140309B CN 201510145499 A CN201510145499 A CN 201510145499A CN 106140309 B CN106140309 B CN 106140309B
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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 group VIB, it is characterized in that, the carrier is the aluminium oxide molding containing anionic surfactant, on the basis of the carrier, the mass fraction of the anionic surfactant is that catalyst described in 0.1%-10% also contains the second organic matter in addition to anionic surfactant, on the basis of catalyst, the mass fraction of second organic matter is 0.1-30%.Compared with prior art, the performance that the present invention provides catalyst is improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method and applications.
Background technique
It is raw that the environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter force oil refining circle more to focus on clean fuel
Technological development is produced, how the production super-low sulfur oil product of economical rationality, which has become, needs weight in oil refining circle's current and expected future regular period
One of the project that point solves.And developing the novel hydrogenation catalyst with more high activity and selectivity then is to produce clear gusoline most
Economic one of method.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hydrogenation catalyst that performance is improved and its applications.
The present invention relates to the following contents:
1. a kind of hydrogenation catalyst is selected from group VIB containing carrier and at least one group VIII and at least one of being selected from
Metal component, which is characterized in that the carrier be the aluminium oxide molding containing anionic surfactant, with the load
On the basis of body, the mass fraction of the anionic surfactant is 0.1%-10%, and the catalyst also contains except anion
The second organic matter outside type surfactant, on the basis of catalyst, the mass fraction of second organic matter is 0.1-30%.
2. the catalyst according to 1, which is characterized in that on the basis of the carrier, the anionic surface activity
The mass fraction of agent is 0.3%-5%, and on the basis of catalyst, the mass fraction of second organic matter is 1-22%.
3. the catalyst according to 1, which is characterized in that the anionic surfactant is selected from carboxylate, sulfuric acid
One or more of ester salt, sulfonate and phosphate ester salt.
4. the catalyst according to 3, which is characterized in that the anionic surfactant is selected from ammonium oleate, oleic acid
One or more of sodium, ammonium stearate, odium stearate, neopelex.
5. the catalyst according to 1, which is characterized in that containing selected from silica, oxidation in the aluminium oxide molding
One or more of titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide adjuvant component, it is described to help on the basis of the carrier
The mass fraction of agent component is 10% or less.
6. the catalyst according to 5, which is characterized in that on the basis of the carrier, the quality point of the adjuvant component
Number is 0.3%-5%.
7. according to catalyst described in 1 or 5, which is characterized in that contain clay and/or molecule in the aluminium oxide molding
Sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is 35% or less.
8. the catalyst according to 7, which is characterized 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, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, and described the
Group vib metal is selected from molybdenum and/or tungsten, and on the basis of the catalyst, the mass fraction of the group VIII metal component is 1-
10%, the mass fraction of vib metals component is 5-40%.
10. the catalyst according to 9, which is characterized in that on the basis of the catalyst, the group VIII metal group
The mass fraction divided is 1.5-6%, and the mass fraction of vib metals component is 10-35%.
11. the catalyst according to 1, which is characterized in that second organic matter is selected from organic carboxyl acid and its ammonium salt
It is one or more.
12. the catalyst according to 11, which is characterized in that the organic carboxyl acid is selected from trans- 1,2- cyclohexanediamine tetrem
Acid, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and apple
One of acid is a variety of.
13. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, special by hydrocarbon ils and catalyst haptoreaction
Sign is that the catalyst is catalyst described in aforementioned 1-12 any one
In the present invention, the aluminium oxide be can be selected from one or more of γ, η, θ, δ and χ, preferably gamma oxidation
Aluminium.The aluminium oxide has the specific surface and pore volume of conventional alumina, and the specific surface of preferential oxidation aluminium is 150-350 meters2/
Gram, further preferably 180-320 meters2/ gram, the preferably Kong Rongwei 0.4-1.1 ml/g of aluminium oxide, further preferably
0.5-0.9 mls/g.They can be commercially available commodity and can also be prepared by any one method in the prior art.For example, can be with
It is by the mixture selected from one or more of hibbsite, monohydrate alumina and amorphous hydroted alumina through forming
And it is made after roasting.
The molding of the aluminium oxide is carried out using customary way, such as the methods of tabletting, spin, extrusion.It is using
When customary way forms, to ensure molding go on smoothly to material to be formed above-mentioned (for example, hibbsite, one
The mixture of one or more of hydrated alumina and amorphous hydroted alumina) in introduce auxiliary agent and be allowed, such as when squeezing
When, suitable peptizing agent, extrusion aid and water can be introduced into material to be formed above-mentioned, extrusion molding later.The glue
Solvent, the type of extrusion aid and dosage may each be this field routine, such as common peptizing agent can be selected from nitric acid, vinegar
One or more of acid, citric acid, formic acid, trichloroacetic acid, hydrochloric acid, malonic acid, the extrusion aid can be selected from sesbania powder, first
One or more of base cellulose, starch, polyvinyl alcohol, polyethanol.
In one preferred embodiment, the aluminium oxide molding is boehmite and/or the vacation of a kind of modification
Boehmite formed, roast after obtained gama-alumina.
The method of the modified boehmite and/or false boehmite includes: (1) by least one alumina hydration
Object roasting, the roasting condition include: that temperature is 300 DEG C -950 DEG C, and the time is -24 hours 0.5 hour；(2) step (1) is obtained
The product of roasting arrived is mixed at least one boehmite and/or false boehmite and water, obtains a kind of mixture；
(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include: that temperature is 60
DEG C -250 DEG C, the time is -48 hours 0.5 hour；(4) product for obtaining step (3) is dry, obtains modified boehmite
And/or false boehmite.
Wherein, it is 300-750 DEG C that the roasting condition of the preferred step (1), which includes: temperature, and the time is 1-24 hours.
The roasting condition of the further preferred step (1) includes: that temperature is 350-650 DEG C, and the time is 2-10 hours.
It is preferred that the product of roasting and at least one boehmite or a false water that the step (2) obtains step (1) 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
The mass ratio of the boehmite of butt meter or false boehmite is 0.1-20.The further preferred step (2) is by step
(1) in the mixture that the product of roasting and at least one boehmite or false boehmite and water obtained is mixed to get,
Solid content in mass be 5%-70%, wherein the product of roasting in terms of butt boehmite or vacation one water it is soft
The mass ratio of aluminium stone is 0.2-12.
When the water content in the mixture is enough to make the mixture slurries (for example, solid content in mass
It is 35% or less) when, the step of filtering is preferably included before the drying of the step (4).
The hydrothermal conditions of the preferred step (3) include: that temperature is 60 DEG C to less than 140 DEG C, time 0.5-
48 hours.The hydrothermal conditions of the further preferred step (3) include: that temperature is 80-120 DEG C, and the time is that 4-24 is small
When.Either, it is more than or equal to 140 DEG C to less than to be equal to that the hydrothermal conditions of the preferred step (3), which include: temperature,
250 DEG C, the time is 0.5-48 hours；The hydrothermal conditions of the further preferred step (3) include: that temperature is 150-
220 DEG C, the time is 4-24 hours.
It is preferred that the drying temperature of the step (4) is 60 DEG C -180 DEG C, drying time is -24 hours 0.5 hour.Further
It is preferred that the drying temperature of the step (4) is 80 DEG C -150 DEG C, 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 vacation boehmite is also known as boehmite, is one kind at 14.5 ° ± 0.5 ° (2 with X-ray diffraction characterization
θ) there is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse.
The boehmite is also known as boehmite, with X-ray diffraction characterization, goes out to be a kind of at 14.5 ° ± 0.5 ° (2 θ)
Existing strongest, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and
55.2 ° occur corresponding to diffraction maximum not available for the false boehmite of (131), (220) and (151) crystal face respectively).
Inventors of the present invention have surprisingly found that by boehmite and/or false boehmite and one or more of warps
300 DEG C -950 DEG C of roastings (heat treatment) 0.5-24 hours, preferably through 300 DEG C -750 DEG C of roastings (heat treatment) 1-24 hours, into one
The hydrated alumina and water that step preferably roasts (heat treatment) 2-10 hours through 350 DEG C -650 DEG C mix, and obtain a kind of mixing
Object, and by the mixture in closed container in 60 DEG C -250 DEG C of hydro-thermal process 0.5-48 hours, be preferable over 80-220 DEG C of hydro-thermal
Processing 4-24 hours, thus the relative crystallinity of modified obtained boehmite and/or false boehmite improves, and thus
The aluminium oxide being fired maintains higher specific surface area and Kong Rong.
In the present invention, when controlling hydro-thermal process temperature is 140 DEG C or more, gained modified product is boehmite；Control
When hydro-thermal process temperature processed is less than 140 DEG C, crystal phase and the starting material of products therefrom are consistent.
In a specific embodiment, preferably make the crystal phase of the modified product and the consistent step of starting material
Suddenly it is 60 DEG C to less than 140 DEG C that the hydrothermal conditions of (3), which include: temperature, and the time is 0.5-48 hours；Further preferred institute
It is 80-120 DEG C that the hydrothermal conditions for stating step (3), which include: temperature, and the time is 1-24 hours.
In another embodiment, preferably make the step (3) of the modified product boehmite
Hydrothermal conditions include: temperature be more than or equal to 140 DEG C to less than be equal to 250 DEG C, the time be 0.5-48 hours；Further
The hydrothermal conditions of the preferred step (3) include: that 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 be with
It is that this is not particularly limited using arbitrary prior art preparation.
Be enough by the hydrated alumina 300 DEG C -950 DEG C of roastings (heat treatment) 1-24 hours, preferably through 300
DEG C -750 DEG C roasting (heat treatment) 1-24 hours, the item further preferably through 350 DEG C of -650 DEG C of roastings (heat treatment) 2-10 hours
Under part, method of roasting described in step (1) is not particularly limited in the present invention.For example, it may be by the hydrated alumina
It is roasted, is also possible in the baking oven or roaster of vacuum-pumping under air atmosphere in usual baking oven or roaster
Under vacuum conditions 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 arbitrary the 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 of 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 600 DEG C constant temperature 4 hours, after roasting the weight of product and roast before the oxidation
The percentage of the weight ratio of aluminium hydrate, the weight of the hydrated alumina before the weight ÷ of product is roasted after butt=roasting
Amount × 100%.
In the present invention, the closed reactor can be arbitrary the reactor that the hydro-thermal reaction can be achieved, for example,
Autoclave etc., the reaction can be to be carried out under static conditions, is also carried out under stirring, preferably under stirring
Carry out hydro-thermal process.
In the present invention, the anionic surfactant is producible hydrophobicity anion chemical combination after a kind of dissociation in water
Object.For example, one or more of 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 in the molding 0.1%-10%, the preferably anionic surfactant of 0.3%-5%
Under the premise of, there is no limit for method of the present invention to the introducing anionic surfactant in the aluminium oxide molding.
In one preferred embodiment, the side of anionic surfactant is introduced in the aluminium oxide molding
Method, comprising: (1) impregnate the aluminium oxide molding, the volume of the maceration extract with the solution containing anionic surfactant
It is 0.5-20, preferably 1-15 with the ratio between the pore volume of the molding；(2) mixture for obtaining dipping is in closed reactor
In 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) product of drying steps (2), the drying condition includes: that temperature is 40 DEG C -250 DEG C, excellent
100 DEG C -180 DEG C are selected as, the time is -24 hours 1 hour, preferably -18 hours 2 hours.
Wherein, the room temperature can be the room temperature in each season in throughout the year, generally 5-40 DEG C.The dipping
The solvent of liquid can be the various solvents that can dissolve the anionic surfactant, preferably water, ammonium hydroxide, ethyl alcohol.
Under the premise of being enough to meet the requirements the content of anionic surfactant in the final molding, the present invention
The content and dipping time of anionic surfactant in maceration extract are not particularly limited.
In the case where being enough to ensure that the heat treatment carries out under air tight condition, the present invention does not have the closed reactor
There are special limitation, common such as autoclave high-pressure reactor.
In the present invention, in the method that is introduced into anionic surfactant in the aluminium oxide molding, step (3) is dry
Purpose be remove impregnation product in solvent, under the premise of being enough to realize the purpose, side of the present invention to the drying
There is no limit for method, such as the method that can be heat drying, is also possible to vacuum drying method.
It, can be containing selected from silica, titanium oxide, magnesia, zirconium oxide, oxygen in the aluminium oxide molding in the present invention
Change one or more of thorium, beryllium oxide adjuvant component, on the basis of the carrier, the mass fraction of the adjuvant component is
10% hereinafter, preferably 0.3%-5%.
When in the molding containing in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide one
Kind or when several adjuvant components, in the preparation process of the molding include introduce selected from silica, titanium oxide, magnesia,
The step of one or more of zirconium oxide, thorium oxide, beryllium oxide adjuvant component, the method for introducing adjuvant component are conventional
Method.For example, it may be will contain selected from one of silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide or several
The mixture warp of one or more of hibbsite, monohydrate alumina and the amorphous hydroted alumina of kind adjuvant component
It is made after forming and roasting.Be also possible to mix aluminium oxide and/or its precursor with the compound containing adjuvant component, after pass through
Molding, drying and roasting obtain.
In the present invention, clay and/or molecular sieve can be contained in the molding, it is described viscous on the basis of the carrier
The mass fraction of soil and/or molecular sieve is 35% hereinafter, preferably 1%-20%.
It include introducing in the preparation process of the molding when containing clay and/or molecular sieve in the molding
The step of clay and/or molecular sieve, the method object conventional method for introducing clay and/or molecular sieve.For example, by the clay
And/or molecular sieve is selected from one or more of hibbsite, monohydrate alumina and amorphous hydroted alumina with described
Mixture after molding and roasting be made.
In the present invention, the clay can selected from kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite,
One of rectorite, sepiolite, attapulgite, hydrotalcite and bentonite are a variety of.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 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecule
Sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta
One of zeolite and omega zeolite are a variety of.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, Titanium Sieve Molecular Sieve and phosphoric acid
One of sial (that is, SAPO) molecular sieve is a variety of.According to the present invention, the molecular sieve is preferably hydrogen type molecular sieve.It is described
Hydrogen type molecular sieve can be commercially available, can also be using conventional method preparation.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 be fired and to form hydrogen type molecular sieve.
The second organic compound organic carboxyl acid and its ammonium salt are selected from trans- 1,2-cyclohexanediaminetetraacetic acid, ethylenediamine tetraacetic
Acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid and its ammonium salt
One of or it is a variety of.
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 group VIB in the catalyst is conventional selection, for example, described
Group VIII metal component is selected from cobalt and/or nickel, and vib metals group is selected from molybdenum and/or tungsten.
In a specific embodiment, on the basis of the catalyst, the group VIII metal component (in terms of oxide,
If nickel is NiO, cobalt CoO) mass fraction be 1-10%, preferably 1.5-6%, vib metals component is (with oxide
Meter, if molybdenum is MoO3, tungsten WO3) mass fraction be 5-40%, preferably 10-35%.
In the present invention, at least one group VIII and at least one vib metals component are introduced in Xiang Suoshu 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 group VIB gold
Belong to compound to be configured to impregnate the method for the carrier after mixed solution；Can be will containing at least one group VIII and at least
A method of selected from vib metals compound individually prepare solution after impregnated carrier.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, be dried, roast or do not roast after the impregnation steps are completed and etc., preferably only do
It is dry, do not roast.The condition of the drying and roasting is conventional, for example, drying temperature is 100-300 DEG C, preferably 100-
280 DEG C, drying time is 1-12 hours, preferably 2-8 hours；Maturing temperature is 350-550 DEG C, preferably 400-500 DEG C, is roasted
Burning the time is 1-10 hours, preferably 2-8 hours.
The group VIII metallic compound is selected from one or more of the soluble compound of these metals, for example,
It can be one or more of the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
Described vib metals compound is selected from one or more of the soluble compound of these metals, for example,
It can be one or more of 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 the hydrotreating reaction condition, there is no particular limitation, and preferred reaction condition includes: anti-
Answer 200-420 DEG C of temperature, further preferably 220-400 DEG C, pressure 2-18 megapascal, further preferably 2-15 megapascal, when liquid
Air speed 0.3-10 hours-1, further preferably 0.3-5 hours-1, hydrogen to oil volume ratio 50-5000, further preferably 50-
4000。
The device of the hydrogenation reaction can be enough to urge the feedstock oil under hydrogenation conditions with described any
It is 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
It is 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 respectively
Kind heavy mineral oil or synthetic oil or their mixed fraction oil, for example it is selected from crude oil, distillate, solvent-refined oil, slack wax, wax
One or more of lower oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.
Compared with prior art, the hydrogenation activity that the present invention provides catalyst is improved, especially by table containing anion
The catalyst of carrier preparation of the use of face activating agent through the modified hydrated alumina preparation of method provided by the invention, it is this to change
Property is particularly evident.
For example, the aluminium oxide molding with provided by the invention containing anionic surfactant and conventional method preparation respectively
Carrier prepare tenor 2.4%NiO and 12%MoO3Hydrobon catalyst C and DC (reference agent).To contain 4,6- bis-
The mixed solution of the n-decane of 0.59 weight % of methyldibenzothiophene (4,6-DMDBT) is raw material, is added to two kinds of catalyst
Hydrogen is desulphurizing activated to be evaluated.With the activity of catalyst DC for 100, the hydrodesulfurization activity of catalyst C is 112.The result shows that
Compared with the prior art provides the catalyst of carrier preparation, the hydrodesulfurization activity for preparing catalyst by present invention offer carrier is bright
It is aobvious to improve.
Specific embodiment
The present invention will be further illustrated in following example, but not thereby limiting the invention.
In following embodiment, analysis measurement is carried out using content of the x-ray fluorescence method to each element in catalyst
(RIPP132-90, referring to: petrochemical egineering analysis method (RIPP test methods), Yang Cui is surely equal to be compiled, Science Press, and 1990,
371-375).X-ray fluorescence test before first by catalyst sample in air atmosphere 450 DEG C roast 6 hours.
The measurement of sample crystal phase, relative crystallinity and mean grain size is referring to " solid catalyst Practical Research method " (Liu
The big volume of Wei Qiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " petrochemical egineering analysis method (RIPP test methods) " (poplar
Kingfisher is fixed, and Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405) in X-ray diffraction method carry out.
Modified boehmite and/or false boehmite used in embodiment 1-10 declaratives carrier, preparation
Method and the alumina support thus prepared.
Hydrated alumina used in experiment are as follows:
CL-A powder (false boehmite powder), opposite relative crystallinity are 100%, grain size 2.9nm, 70 weight of butt
% is measured, middle petrochemical industry Chang Ling catalyst branch is purchased from.
CL-B powder (boehmite), opposite relative crystallinity are 100%, grain size 5.2nm, 78 weight % of butt,
Purchased from middle petrochemical industry Chang Ling catalyst branch).
CL-C powder (gibbsite (α-Al2O3·3H2O)), opposite relative crystallinity is 100%, grain size 156nm, is done
65 weight % of base is purchased from middle petrochemical industry Chang Ling catalyst branch.
Wherein, 10000 grams of CL-A powder are weighed, with 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 item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in sky
Under gas atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-A-Al2O3.Pass through X-ray diffraction method table
Its crystal phase, crystallinity and grain size are levied, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong,
The results are shown in Table 2.
10000 grams of CL-B powder are weighed, with 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 item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere
Under in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-B-Al2O3.Its crystalline substance is characterized by X-ray diffraction method
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, as a result arranges
In table 2.
It is obtained according to the step (1) in the method for modified boehmite of the present invention and/or false boehmite
Product of roasting are as follows:
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 within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
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 within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
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 within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
CL-A-350: 10000 grams of CL-A powder are weighed and are raised in a nitrogen atmosphere with 3 DEG C/min of heating rate in baking oven
350 DEG C, and CL-A-350 is obtained within constant temperature 4 hours at 350 DEG C.
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 within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
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 within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
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 within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
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 within constant temperature 4 hours to 350 DEG C, and at 350 DEG C.
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 constant temperature 4 hours at 600 DEG C.
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 constant temperature 6 hours at 450 DEG C.
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 constant temperature 6 hours at 400 DEG C.
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 constant temperature 6 hours at 350 DEG C.
Embodiment 1
120 grams of 350 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of A powder is 0.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 160 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S1.Pass through
X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S1.Its crystal 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 measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Embodiment 2
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S2.Pass through X-ray
Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 3
Weigh respectively in terms of butt 464 grams of 109 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 4.25), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S3.Pass through X-ray
Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Formed alumina provided by the invention and its preparation:
Q-S3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, 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
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 250 grams of powder, 180 grams of CL-A-600 powder
8.10) they and 3600 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S4.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S4 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, 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
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 450 300 grams of powder, 10 grams of CL-A-600 powder
4.36) they and 3100 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 60 DEG C of constant temperature are heated to after closed 48 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S5.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S5 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, 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
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 400 grams of powder, 20 grams of CL-A-600 powder
10.29) they and 3200 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 100 DEG C of constant temperature are heated to after closed 24 hours；It is down to room temperature and after filtering,
Filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S6.It is characterized by X-ray diffraction method
Crystal phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S6 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, 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
(total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 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 are heated to after closed 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains through changing
The hydrated alumina Q-S7 of property.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result arranged
In table 1.
Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S7.Its crystal 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 measures its specific surface area and Kong Rong, 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
(total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 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 are heated to after closed 4 hours.It is cooled to room temperature, high pressure kettle cover is opened, 11.75 grams of ammonium dihydrogen phosphates are added,
Room temperature continues stirring 24 hours, after filtering, filter cake is 8 hours dry in 120 DEG C, obtains the modified oxygen containing auxiliary agent phosphorus
Change aluminium hydrate Q-S8.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result listed in table 1
In.
Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S8.Its crystal 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 measures its specific surface area and Kong Rong, and the results are shown in Table 2.It is glimmering using X
Light method measures the content of adjuvant component, and the mass fraction of the phosphate builder based on the element is 0.41%.
Embodiment 9
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues stirring 24 hours, then filters.By filter cake through 120 DEG C
It is 8 hours dry, obtain the modified hydrated alumina Q-S9 containing auxiliary agent titanium.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S9 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.The content of adjuvant component, the titanium based on the element are measured using X-fluorescence method
The mass fraction of auxiliary agent is 3.12%.
Embodiment 10
320 grams of 230 grams of CL-B powder, CL-A-450 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of B powder is 1.39), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 200 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S10.It is logical
It crosses X-ray diffraction method and characterizes its crystal phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S10.Its crystal 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 measures its specific surface area and Kong Rong, 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 CL-A powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；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；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-1.
Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
QBF-1 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S11 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal 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 Kong Rong, 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
In the autoclave for the stainless steel band polytetrafluoro liner that volume with stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；Drop
It is to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-2.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S12 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal 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 Kong Rong, the results are shown in Table 2.
Embodiment 13
470 grams of CL-B powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；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；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-3.
Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
QBF-3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S13 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal 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 Kong Rong, the results are shown in Table 2.
Table 1
Wherein, when measuring the crystallinity of false boehmite, using CL-A powder as standard specimen；In the knot of measurement boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When measuring gama-alumina crystallinity, with CL-B-Al2O3For standard specimen.
Table 2
| Embodiment | Aluminium oxide | Specific surface area, m2/g | Kong Rong, 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 carrier of offer of the present invention, i.e., the aluminium oxide containing anionic surfactant at
Type object and preparation method thereof.
Embodiment 14
1 200 grams of carrier S are weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 2 milliliters of 25% concentrated ammonia liquors of mass fraction, 130 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 90 DEG C constant temperature 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S1 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 15
2 200 grams of carrier S are weighed to be placed in autoclave；1.66 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 2 milliliters of 25% concentrated ammonia liquors of mass fraction, 130 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in being placed at room temperature for 48 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S2 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 16
3 200 grams of carrier S are weighed to be placed in autoclave；3.58 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 6 milliliters of 25% concentrated ammonia liquors of mass fraction, 130 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 60 DEG C constant temperature 18 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S3 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 17
4 200 grams of carrier S are weighed to be placed in autoclave；1.08 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 3 milliliters of 25% concentrated ammonia liquors of mass fraction, 140 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 120 DEG C constant temperature 6 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S4 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 18
5 200 grams of carrier S are weighed to be placed in autoclave；0.77 gram of ammonium oleate is dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 2.5 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to height
Press kettle in, it is closed after in 160 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic table
The aluminium oxide molding R-S5 of face activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 19
6 200 grams of carrier S are weighed to be placed in autoclave；4.55 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 8 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 180 DEG C constant temperature 2 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S6 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 20
7 200 grams of carrier S are weighed to be placed in autoclave；4.93 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 110 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S7 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 21
8 200 grams of carrier S are weighed to be placed in autoclave；4.31 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 120 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S8 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 22
9 200 grams of carrier S are weighed to be placed in autoclave；4.46 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 130 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S9 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 23
10 200 grams of carrier S are weighed to be placed in autoclave；1.05 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 80 DEG C constant temperature 10 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S10 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 24
11 200 grams of carrier S are weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 90 DEG C constant temperature 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S11 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 25
12 200 grams of carrier S are weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 90 DEG C constant temperature 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding R-S12 of activating agent.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 26
13 200 grams of carrier S are weighed to be placed in autoclave；1.25 grams of ammonium oleates are dissolved in 200 milliliters of ammonium hydroxide-ethanol solution
(by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), is then added to high pressure
In kettle, it is closed after in 90 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing anionic surface
The aluminium oxide molding 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 ammonium hydroxide-ethanol solution
200 milliliters (by 12 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water, is mixed), then plus
Enter into autoclave, it is closed after in 90 DEG C constant temperature 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, obtain containing it is negative from
The aluminium oxide molding R-S14 of subtype surfactant.The mass fraction of anionic surfactant is listed in table 3 in carrier.
Embodiment 28
The modified aluminas hydrate Q-S2 powder of preparation and 2 equivalent of embodiment, then with 25 grams of silicon dioxide powders (in being purchased from
Petrochemical industry Chang Ling catalyst branch) mixing after 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 item that circumscribed circle diameter is 1.6 millimeters, it is 4 hours dry through 120 DEG C, finally in air atmosphere
Be raised to 600 DEG C in Muffle furnace with 4 DEG C/min of heating rate, then 600 DEG C constant temperature 4 hours, obtain alumina support S14.
It weighs 14 200 grams of carrier S to be placed in autoclave, by 5.25 grams of ammonium oleates and 0.89 gram of neopelex
Be dissolved in 200 milliliters of ammonium hydroxide-ethanol solution (by 13 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of dehydrated alcohols, surplus is water,
Mix), be then added in autoclave, it is closed after in 100 DEG C constant temperature 2 hours.By sample in 120 DEG C dry 4 after cooling
Hour, obtain the aluminium oxide molding R-S15 containing anionic surfactant.Anionic surfactant in carrier
Mass fraction is listed in table 3.
Embodiment 29
The hydrated alumina Q-S2 powder of preparation and the modification of 2 equivalent of embodiment, then with 36 grams of Hydrogen Y molecular sieve powder
(Na2O content 0.2%, cell parameter 2.464, relative crystallinity 88%, be purchased from middle petrochemical industry Chang Ling catalyst branch) mixing after
Being extruded into circumscribed circle diameter with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is 1.6
The cloverleaf pattern item of millimeter, it is 4 hours dry through 120 DEG C, finally in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 600 DEG C, then 600 DEG C constant temperature 4 hours, obtain alumina support S15.
15 200 grams of carrier S are 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 ammonium hydroxide-ethanol solution (by 15 milliliters of 25% concentrated ammonia liquors of mass fraction, 150 milliliters of anhydrous second
Alcohol, surplus are water, are mixed), be then added in autoclave, it is closed after in 100 DEG C constant temperature 3 hours.By sample after cooling
It is 4 hours dry in 120 DEG C, obtain the aluminium oxide molding R-S16 containing anionic surfactant.Anionic in carrier
The mass fraction of surfactant is listed in table 3.
Embodiment 30-48 illustrates catalyst provided by the invention and its preparation.
Embodiment 30-45
Respectively with the ammonium hydroxide containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of ethylenediamine tetra-acetic acids
199 milliliters of solution dipping embodiments 14~29 be prepared R-S1, R-S2, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8,
R-S9, R-S10, R-S11, R-S12, R-S13, R-S14, R-S15 and R-S16, dip time 2 hours, later impregnation product in
120 DEG C drying 4 hours, obtain catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and
C16。
Embodiment 46
With containing 34.96 grams of ammonium heptamolybdates, 1.28 grams of trans- 1,2-cyclohexanediaminetetraacetic acid, 3.56 grams of ethylenediamine tetra-acetic acids,
199 milliliters of dipping embodiments 14 of ammonia spirit of 2.58 grams of malic acid, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates are prepared into
The R-S1 arrived, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates, 12.27 grams of second
199 milliliters of the ammonia spirit above-mentioned carriers of dipping of ethylenediamine tetraacetic acid (EDTA) and 3.26 grams of ammonium oxalate, dip time 2 hours, impregnate later
Product is 4 hours dry in 120 DEG C, obtains catalyst C17.
Embodiment 47
With containing 34.96 grams of ammonium heptamolybdates, 0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acids, 1.56 grams of formic acid, 6.98 grams of lemons
The R-S1 that 199 milliliters of ammonia spirit dipping embodiments 14 of sour ammonium and 36.23 grams of citric acids are prepared, later impregnation product in
120 DEG C drying 4 hours；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates, 21.27 grams of ethylenediamine tetra-acetic acids and 1.86 grams of amino
199 milliliters of the ammonia spirit above-mentioned carriers of dipping of triacetic acid, dip time 2 hours, impregnation product was small in 120 DEG C of dryings 4 later
When, obtain catalyst C18.
Embodiment 48
It is prepared into 199 milliliters of dipping embodiments 14 of ammonia spirit containing 34.96 grams of ammonium heptamolybdates and 22.51 grams of citric acids
The R-S1 arrived, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates and 23.27 grams
199 milliliters of the ammonia spirit above-mentioned carriers of dipping of ethylenediamine tetra-acetic acid, dip time 2 hours, impregnation product was dry in 120 DEG C later
Dry 4 hours, obtain catalyst C19.
Comparative example 1-5 illustrates comparative catalyst and its preparation.
Comparative example 1
11 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two
199 milliliters of dippings of ammonia spirit of amine tetraacethyl impregnate above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, are catalyzed
Agent D1.
Comparative example 2
12 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two
199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of amine tetraacethyl, it is then 4 hours dry at 120 DEG C, obtain catalyst D2.
Comparative example 3
13 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two
199 milliliters of dippings of ammonia spirit of amine tetraacethyl impregnate above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, are catalyzed
Agent D3.
Comparative example 4
Weigh support C L-A-Al2O3200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15
199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of gram ethylenediamine tetra-acetic acid, it is then 4 hours dry at 120 DEG C, it is urged
Agent D4.
Comparative example 5
With the 199 milliliters of dipping embodiments 14 of ammonia spirit for containing 34.96 grams of ammonium heptamolybdates and 22.62 grams of Nickelous nitrate hexahydrates
The R-S1 being prepared 2 hours, it is then 4 hours dry at 120 DEG C, obtain catalyst D5.
Catalyst performance evaluation
It evaluates embodiment 30-48 and the hydrodesulfurization performance for the comparative catalyst that catalyst and comparative example 1-5 are provided is provided,
As a result it is listed in table 3.
Evaluating catalyst is with the mixed of the n-decane containing 4,6-- dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 weight %
Conjunction solution is raw material, is evaluated in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation company, model: DADI)
Catalyst breakage is the particle of 40-60 mesh at diameter by the hydrodesulfurization activity of catalyst, and the loadings of catalyst are 0.15
Gram.Before formal charging, presulfurization first is carried out to catalyst respectively using the hexamethylene containing 6 weight % carbon disulfide as sulfurized oil,
The condition of presulfurization includes: that pressure is 4.14MPa, and temperature is 362 DEG C, and the time is 3.5 hours, and sulfurized oil feed rate is 0.2
Ml/min.After vulcanization, being cooled to reaction temperature is 280 DEG C, cuts raw material.Reaction condition includes: raw material feed rate
For 0.2 ml/min, pressure 4.14MPa, hydrogen to oil volume ratio 900.Reaction takes after 3 hours in high-pressure separator exit
Sample.Gained sample is analyzed with Agilent6890N gas chromatograph.Wherein, the hydrodesulfurization activity A of 4,6-DMDBT is pressed
Formula calculates:
A=ln [100/ (100-X)],
In formula, the desulfurization degree of X 4,6-DMDBT (circular of X referring to " catalysis journal ", 2002,23 (3):
271-275)。
The hydrodesulfurization activity for taking 4, the 6-DMDBT of comparative catalyst D1 is 100, then opposite the 4,6- of other catalyst
The hydrodesulfurization activity of DMDBT 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
By table 3 the results show that hydrogenation catalyst according to the present invention shows higher hydrodesulfurization activity.
Claims (11)
1. a kind of hydrogenation catalyst, containing carrier and at least one it is selected from group VIII and at least one gold selected from group VIB
Belong to component, which is characterized in that the carrier is the aluminium oxide molding containing anionic surfactant, is with the carrier
The mass fraction of benchmark, the anionic surfactant is 0.1%-10%, and the catalyst also contains except anionic surface
The second organic matter outside activating agent, on the basis of catalyst, the mass fraction of second organic matter is 0.1-30%；
The anionic surfactant is selected from one or more of carboxylate, sulfuric acid, sulfonate and phosphate ester salt；
Second organic matter is selected from the one or more of organic carboxyl acid and its ammonium salt.
2. catalyst according to claim 1, which is characterized in that on the basis of the carrier, the anionic surface
The mass fraction of activating agent is 0.3%-5%, and on the basis of catalyst, the mass fraction of second organic matter is 1-22%.
3. catalyst according to claim 1, which is characterized in that the anionic surfactant be selected from ammonium oleate,
One or more of enuatrol, ammonium stearate, odium stearate, neopelex.
4. catalyst according to claim 1, which is characterized in that in the aluminium oxide molding containing selected from silica,
One or more of titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide adjuvant component, on the basis of the carrier, institute
The mass fraction for stating adjuvant component is 10% or less.
5. catalyst according to claim 4, which is characterized in that on the basis of the carrier, the matter of the adjuvant component
Amount score is 0.3%-5%.
6. catalyst according to claim 1 or 4, which is characterized in that in the aluminium oxide molding containing clay and/or
Molecular sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is 35% or less.
7. catalyst according to claim 6, which is characterized in that on the basis of the carrier, the clay and/or molecule
The mass fraction of sieve is 1%-20%.
8. catalyst according to claim 1, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, and described the
Group vib metal is selected from molybdenum and/or tungsten, and on the basis of the catalyst, the mass fraction of the metal component of group VIII is 1-
10%, the mass fraction of metal component of group VIB is 5-40%.
9. catalyst according to claim 8, which is characterized in that on the basis of the catalyst, the group VIII metal
The mass fraction of component is 1.5-6%, and the mass fraction of metal component of group VIB is 10-35%.
10. catalyst according to claim 1, which is characterized in that the organic carboxyl acid is selected from trans- 1,2- cyclohexanediamine
Tetraacethyl, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and
One of malic acid is a variety of.
11. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, by hydrocarbon ils and catalyst haptoreaction, feature exists
In the catalyst is catalyst described in claim 1-10 any one.
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|---|---|---|---|---|
| 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 |
| 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 |
| CN103100390A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103100390A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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