CN106140316B - A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation - Google Patents
A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation, the hydrogenation catalyst contains aluminium oxide shaping carrier containing adjuvant component, organic compound, at least one is selected from group VIII and at least one metal component selected from group VIB, it is characterized in that, the aluminium oxide shaping carrier containing adjuvant component is obtained by a kind of boehmite of modification containing adjuvant component and/or false boehmite after being molded, roasting, and the boehmite containing adjuvant component and/or false boehmite are prepared by method comprising the following steps：(1) at least one hydrated alumina is roasted；(2) product of roasting that step (1) obtains is mixed at least one boehmite and/or false boehmite, the compound containing adjuvant component and water, obtains a kind of mixture；(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor；(4) product for obtaining step (3) is dried.Compared with prior art, the catalytic performance of present invention offer hydrogenation catalyst is improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, the applications of the preparation method of the catalyst and the catalyst.
Background technology
The environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter 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, which has become, needs weight in oil refining circle's current and expected future regular period
One of the project that point solves.And develop the novel hydrogenation catalyst with higher hydrodesulfurization activity and direct desulfurization selectivity then
Reactive hydrogen consumption can be reduced.
The activity and selectivity for improving hydrogenation catalyst seeks to improve the dispersity of metal on the alumina support, and
The generation of low hydrogenation active metals phase species is avoided as far as possible.Important component of the alumina support as hydrogenation catalyst
One of, the catalytic performance important of surface physico-chemical property and pore structure parameter to hydrogenation catalyst.And prepare oxygen
The presoma for changing alumina supporter is mainly false boehmite and boehmite, object of the physical and chemical indexes to finished product alumina support
Changing property has significant impact.
In addition, the hydrodesulfurization that can also improve catalyst by introducing organic matter in hydrogenation catalyst preparation process is lived
Property, for example, CN200910177170.6 provides a kind of hydrogenation catalyst and preparation method thereof, including step：(1) with containing molybdenum
And/or the solution impregnating carrier of Thermal stability of the tungsten with atom；(2) impregnation product of drying steps (1)；(3) with nickeliferous
And/or the product of the mixed solution impregnation steps (2) of cobalt, organic acid and ammonium ion；(4) impregnation product of drying steps (3)；
Wherein, it is counted by oxide and on the basis of catalyst, the Thermal stability for matching atom containing molybdenum and/or tungsten in the step (1)
Aqueous solution and nickeliferous and/or cobalt in the step (3), organic acid and ammonium ion mixed solution in each component concentration
The content of molybdenum and/or tungsten is set in final catalyst to be 9~30 weight % with the dosage of described two solution, nickel and/or cobalt contain
Amount is 0.5~8 weight %.The ammonium salt of the organic acid is ammonium citrate, ammonium oxalate, ammonium tartrate, aminotriacetic acid ammonium, apple
It is one or more in sour ammonium and ethylenediamine tetra-acetic acid ammonium.Compared with the catalyst that the prior art provides, what which provided urges
Agent hydrodesulfurization activity is high.
Invention content
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 contains the aluminium oxide shaping carrier containing adjuvant component, organic compound, at least one choosing
From group VIII and at least one metal component selected from group VIB, which is characterized in that the aluminium oxide containing adjuvant component at
Type carrier is obtained by a kind of boehmite of modification containing adjuvant component and/or false boehmite after being molded, roasting, with
On the basis of the butt of the boehmite containing adjuvant component and/or false boehmite, the auxiliary agent group based on the element
The mass fraction divided is 0.1%-10%, and the adjuvant component is selected from IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB
One or more of, the boehmite containing adjuvant component and/or false boehmite are by the side that includes the following steps
It is prepared by method：
(1) at least one hydrated alumina is roasted, the roasting condition includes：Temperature is 300 DEG C -950 DEG C, the time
It is -24 hours 0.5 hour；
(2) by product of roasting that step (1) obtains and at least one boehmite and/or false boehmite, containing helping
The compound and water of agent component mix, and obtain a kind of mixture；
(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include：
Temperature is 60 DEG C -250 DEG C, and the time is -48 hours 0.5 hour；
(4) product for obtaining step (3) is dried.
2. according to the catalyst described in aforementioned 1, which is characterized in that the adjuvant component be selected from fluorine, phosphorus, boron, silicon, magnesium, zinc,
One or more of lanthanum, cerium, titanium and zirconium, with the dry of the boehmite containing adjuvant component and/or false boehmite
On the basis of base, the mass fraction of the adjuvant component based on the element is 0.3%-5%.
3. according to the catalyst described in aforementioned 1, which is characterized in that the roasting condition of the step (1) includes：Temperature is
300-750 DEG C, further preferably 350-650 DEG C, time are 1-24 hours, further preferably 2-10 hours.
4. according to the catalyst described in aforementioned 1, which is characterized in that the hydrothermal conditions of the step (3) include：Temperature
It it is 60 DEG C to less than 140 DEG C, further preferably 80-120 DEG C, the time is 0.5-48 hours, further preferably 4-24 hours.
5. according to the catalyst described in aforementioned 1, which is characterized in that the hydrothermal conditions of the step (3) include：Temperature
For be more than or equal to 140 DEG C to less than be equal to 250 DEG C, further preferably 150-220 DEG C, the time be 0.5-48 hours, further
Preferably 4-24 hours.
6. according to the catalyst described in aforementioned 1, which is characterized in that the drying temperature of the step (4) is 60 DEG C -180 DEG C,
Further preferably 80 DEG C -150 DEG C, drying time is -24 hours 0.5 hour, further preferably -12 hours 1 hour.
7. according to the catalyst described in aforementioned 1, which is characterized in that the hydrated alumina is selected from boehmite, vacation
One or more of boehmite, hibbsite.
8. according to the catalyst described in aforementioned 7, which is characterized in that the hibbsite is gibbsite.
9. according to the catalyst described in aforementioned 1, which is characterized in that the product of roasting that the step (2) obtains step (1)
In the mixture being mixed to get at least one boehmite or false boehmite and water, solid content in mass is
1%-80%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.1-
20。
10. according to the catalyst described in aforementioned 9, which is characterized in that the roasting that the step (2) obtains step (1) is produced
In the mixture that object is mixed to get at least one boehmite or false boehmite and water, solid content in mass
For 5%-70%, wherein the mass ratio of the product of roasting and boehmite in terms of butt or false boehmite is
0.2-12。
11. according to the catalyst described in aforementioned 1, which is characterized in that the group VIII metal component be selected from nickel and/or
The metal component of cobalt, group VIB is selected from molybdenum and/or tungsten, and on the basis of catalyst, the content of the group VIII metal component is
The content of 1-10 weight %, vib metals component are 5-40 weight %.
12. according to the catalyst described in aforementioned 11, which is characterized in that on the basis of catalyst, the group VIII metal
The content of component is 1.5-6 weight %, and the content of vib metals component is 10-35 weight %.
13. according to the catalyst described in aforementioned 1, which is characterized in that the organic compound is selected from organic carboxyl acid, organic carboxylic
One or more of the ammonium salt of acid, on the basis of catalyst, the content of the organic compound is 0.1-30 weight %.
14. according to the catalyst described in aforementioned 13, 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 or more of malic acid, on the basis of catalyst, the content of the organic compound is 1-20 weight %.
15. catalyst according to claim 1, which is characterized in that contain clay in the aluminium oxide shaping carrier
And/or molecular sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is 35% or less.
16. catalyst according to claim 15, which is characterized in that on the basis of the carrier, the clay and/
Or the mass fraction of molecular sieve is 1%-20%.
17. 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 the catalyst described in aforementioned any one.
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 characterized with X-ray diffraction, to be a kind of at 14.5 ° ± 0.5 ° (2
θ) there is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse.
The boehmite is also known as boehmite, is characterized with X-ray diffraction, goes out at 14.5 ° ± 0.5 ° (2 θ) for one kind
Existing strongest, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and
Diffraction maximum not available for 55.2 ° of false boehmites occurred respectively corresponding to (131), (220) and (151) 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 -950 DEG C roast (heat treatment) 0.5-24 hours, preferably (heat treatment) 1-24 hours are roasted through 300 DEG C -750 DEG C, into one
Step preferably through 350 DEG C -650 DEG C roast the hydrated alumina of (heat treatment) 2-10 hours, the compound containing adjuvant component and
Water mixes, and obtains a kind of mixture, and by the mixture in closed container in 60 DEG C of -250 DEG C of hydro-thermal process 0.5-48 hours,
It is preferable over 80-220 DEG C of hydro-thermal process 4-24 hours, thus the phase of modified obtained boehmite and/or false boehmite
Crystallinity is improved, and thus fired obtained aluminium oxide maintains higher specific surface area and Kong Rong.
In a specific embodiment, the product of roasting that the step (2) obtains step (1) and the soft aluminium of at least one water
In the mixture that stone or false boehmite and water are mixed to get, solid content preferably in mass is 1%-80%, wherein
The mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.1-20.Further preferred institute
Step (2) is stated to mix the product of roasting that step (1) obtains at least one boehmite or false boehmite and water
In obtained mixture, solid content in mass is 5%-70%, wherein the product of roasting and the water in terms of butt are soft
The mass ratio of aluminium stone or false boehmite is 0.2-12.
When the water content in the mixture is enough to make the mixture to be slurries (for example, solid content in mass
It is 35% or less) when, the step of preferably including to filter before the drying of the step (4).
Wherein, when it is 140 DEG C or more to control hydro-thermal process temperature, gained modified product is boehmite；Control water
When heat treatment temperature is less than 140 DEG C, crystalline phase and the starting material of products therefrom are consistent.
In a specific embodiment, the step for preferably making the crystalline phase of the modified product consistent with starting material
Suddenly the hydrothermal conditions of (3) include：Temperature is 60 DEG C to less than 140 DEG C, and the time is 0.5-48 hours；Further preferred institute
The hydrothermal conditions for stating step (3) include：Temperature is 80-120 DEG C, and the time is 1-24 hours.
In another embodiment, it is the step (3) of boehmite preferably to make the modified product
Hydrothermal conditions include：Temperature is more than or equal to 140 DEG C to less than equal to 250 DEG C, and the time is 0.5-48 hours；Further
Preferably the hydrothermal conditions of the step (3) 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 use arbitrary prior art preparation, this is not particularly limited.
It is being enough the hydrated alumina roasting (heat treatment) 1-24 hours at 300 DEG C -950 DEG C, preferably through 300
DEG C of -750 DEG C roastings (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, the method for 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 under air atmosphere in usual baking oven or roaster, can also be in the baking oven or roaster of vacuum-pumping
Under vacuum or it is passed through under inert gas conditions and carries out.When the roasting is passed through inert gas, the inert gas can
To be 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 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 arbitrary the reactor of the 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 one kind of the adjuvant component in IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB
Or several, one or more of fluorine, phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium preferably wherein.By the institute in terms of butt
On the basis of stating boehmite and/or false boehmite containing adjuvant component, the quality of the adjuvant component based on the element
Score is 0.1%-10%, preferably 0.3-5%, further preferably 0.3-4%.
The compound containing adjuvant component, preferably their water soluble compound, the example of this compound is such as：Hydrogen fluorine
Acid, ammonium fluoride, hydrofluoric acid ammonium, fluosilicic acid, ammonium fluosilicate, boric acid, ammonium borate, ammonium metaborate, tetraboric acid ammonium, phosphoric acid, ammonium phosphate,
Ammonium hydrogen phosphate, ammonium dihydrogen phosphate, boric acid, tetraboric acid ammonium, Ludox, silicon tetrachloride, ammonium fluosilicate and ethyl orthosilicate, nitric acid
Magnesium, magnesium acetate, magnesium sulfate, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, nitre
Sour lanthanum, lanthanum carbonate, lanthanum chloride, cerous nitrate, cerous carbonate, cerium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, butyl titanate,
Zirconium nitrate, zirconyl nitrate and zirconium oxychloride etc..
Compared with prior art, the modification boehmite and/or the soft aluminium of a false water that method provided by the present invention obtains
Stone is improving relative crystallinity simultaneously, can effectively inhibit the growth of crystal grain, be realized to a certain extent to modified product crystal grain
The regulation and control of growth.High-specific surface area and Kong Rong can be obtained after the modification boehmite and/or false boehmite are fired
Alumina support.
The organic compound is selected from one or more of organic carboxyl acid and its ammonium salt, described on the basis of catalyst
The content of organic compound is 0.1-30 weight %.It is preferred that the organic carboxyl acid is selected from trans- 1,2-cyclohexanediaminetetraacetic acid, second
In ethylenediamine tetraacetic acid (EDTA), aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid
One or more, on the basis of catalyst, the content of the organic compound is 1-20 weight %.
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, catalyst of the present invention is preferably comprised with oxide
The group VIII metal component of the 1-10 weight % of (such as NiO, CoO) meter, further preferably 1.5-6 weight %, containing with oxygen
Compound (such as MoO3, WO3) meter 5-40 weight % vib metals component, further preferably 10-35 weight %.
In the present invention, the organic compound, at least one group VIII and at least one vib metals component are born
It is method customary in the art to be loaded in method on carrier, for example, it may be by organic compound, containing group VIII and/or the
Group vib metallic compound is configured to impregnate the method for the carrier after solution；It can be by organic compound, contain group VIII
Or the method that vib metals compound individually prepares impregnated carrier after solution.Wherein, pass through the solution to metallic components
The adjusting and control of concentration, dosage or carrier dosage, can prepare the catalyst of specified content, this is art technology
What personnel were readily appreciated by.
According to the present invention, after the impregnation steps are completed, it the steps such as can optionally be dried, roast or do not roast
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；Calcination temperature is 350-550 DEG C, and preferably 400-500 DEG C, roasting time is
1-10 hours, preferably 2-8 hours.
The dipping be prepare catalyst customary way, for example, it may be spray process impregnate, saturation dipping method and
Excessive liquid dipping method.
In the present invention, clay and/or molecular sieve can be contained in the aluminium oxide shaping carrier, using the carrier as base
The mass fraction of standard, the clay and/or molecular sieve is 35% hereinafter, preferably 1%-20%.
When containing clay and/or molecular sieve in the aluminium oxide shaping carrier, in the system of the aluminium oxide shaping carrier
Include the steps that introducing clay and/or molecular sieve during standby, the method object routine side for introducing clay and/or molecular sieve
Method.For example, the clay and/or molecular sieve are selected from hibbsite, monohydrate alumina and amorphous hydrogen-oxygen with described
The mixture for changing one or more of aluminium is made after molding and roasting.
In the present invention, the clay can be selected from kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite,
It is one or more in rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.The molecular sieve can be zeolite molecules
Sieve and/or non-zeolite molecular sieve.The zeolite molecular sieve can be erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite,
ZSM-11 zeolites, ZSM-22 zeolites, ZSM-23 zeolites, ZSM-35 zeolites, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecules
Sieve, ZSM-4 molecular sieves, ZSM-18 molecular sieves, ZSM-20 molecular sieves, ZSM-48 zeolites, ZSM-57 zeolites, faujasite, Beta
It is one or more in zeolite and omega zeolite.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, Titanium Sieve Molecular Sieve and phosphoric acid
It is one or more in sial (that is, SAPO) 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 commercially available, conventional method can also be used to prepare.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 catalyst, the content of carrier is well known to those skilled in the art.On the basis of the total amount of catalyst, with
Oxide meter, the content of carrier can be 60-90.5 weight % in the catalyst.
The group VIII metallic compound is selected from one or more of the soluble compound of these metals, for example,
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,
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：Instead
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 any can be enough that the feedstock oil is made to urge with described under hydrogenation conditions
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 each
Kind of heavy mineral oil or synthetic oil or their mixed fraction oil, for example, selected from crude oil, distillate (gasoline, kerosene, diesel oil etc.),
Solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and one kind or several in heavy deasphalted oil
Kind.
In the present invention, the direct desulfurization refers to thiophene sulfocompounds, without owning on saturation sulfur heterocyclic ring in advance
Carbon-carbon double bond, and the sulphur atom on sulfur heterocyclic ring is directly realized into desulfurization by hydrogenolysis.For example, it is generally believed that dibenzo thiophene
The hydrodesulfurization reaction of pheno is carried out according to two kinds of reaction paths：Path I is the sulphur atom in direct removing dibenzothiophenes molecule
Generate biphenyl, referred to as direct desulfurization (or hydrogenolysis desulfurization)；Path II is that first the benzene ring hydrogenation to dibenzothiophenes generates hexahydro two
Benzothiophene, then the sulphur atom removed in hexahydro dibenzothiophenes molecule generate cyclohexyl benzene, referred to as pre- hydrodesulfurization.It improves and adds
The direct desulfurization of hydrogen catalyst selectively will be helpful to reduce unnecessary carbon-carbon double bond in oil hydrogenation sweetening process and add hydrogen full
With, to reduce hydrogen consumption.
Compared with existing catalyst, aluminium oxide provided by the invention is that catalyst prepared by carrier has preferably plus hydrogen is de-
Sulphur activity and higher direct desulfurization selectivity.
For example, the mixed solution of the n-decane to contain 0.58 weight % of dibenzothiophenes (DBT) puies forward the present invention as raw material
The catalyst of confession and comparative catalyst carry out hydrodesulfurization activity comparative evaluation, with the hydrodesulfurization activity of comparative catalyst and directly
It is 100 to connect desulfuration selectivity, then the opposite hydrodesulfurization activity that the present invention provides catalyst is 115, relatively direct desulfurization choosing
Selecting property is up to 114.Obviously, increased with the selectivity of direct desulfurization with desulphurization reaction, it will help reduce oil hydrogenation desulfurization
Unnecessary carbon-carbon double bond adds hydrogen to be saturated in the process, and generated direct result is exactly to make the hydrogen of desulphurization reaction consume to reduce.
Specific implementation mode
The present invention will be further illustrated in following example, but not thereby limiting the invention.
In the present invention, the measurement reference of sample crystalline phase, crystallinity and mean grain size《Solid catalyst Practical Research side
Method》(the big volume of Liu Weiqiao, Sun Gui, Sinopec publishing house, 2000,57-89) and《Petrochemical analysis method (the experiment sides RIPP
Method)》X-ray diffraction method in (Yang Cuiding, Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405).
The content of adjuvant component is measured using X-fluorescence method.
The hydrated alumina used in experiment is：
CL-A powder (false boehmite powder), relative crystallinity 100%, grain size 2.9nm, 70 weight % of butt,
Purchased from sinopec Chang Ling catalyst branch.
CL-B powder (boehmite), relative crystallinity 100%, grain size 5.2nm, 78 weight % of butt are purchased from
Sinopec Chang Ling catalyst branch).
CL-C powder (gibbsite (α-Al2O3·3H2O)), relative crystallinity 100%, grain size 156nm, butt 65
Weight % is purchased from sinopec Chang Ling catalyst branch.
10000 grams of CL-A 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 of constant temperature 4 hours, obtain alumina support CL-A-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.
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 of 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.
The product of roasting obtained according to the step (1) in the method provided by the present invention 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.
Modified boehmite and/or false boehmite used in embodiment 1-10 declaratives carriers, prepare
Method and the alumina support thus prepared.
Embodiment 1
110 grams of 364 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 0.30), they to be mixed with 3600 grams of deionized waters, and 10.78 grams of ammonium dihydrogen phosphates are added, stirring
At slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, are added after closed
Heat was to 160 DEG C of constant temperature 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain the water containing auxiliary agent
Close aluminium oxide Q-S1.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
By Q-S1 banded extruder (manufacturers：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 in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S1.It is big that its crystalline phase, crystallinity and crystal grain are characterized by X-ray diffraction method
Small, 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 296 grams of 235 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 1.26), they to be mixed with 3600 grams of deionized waters, and 12.08 grams of ammonium dihydrogen phosphates are added, and is stirred
Mix slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, after closed
It is heated to 160 DEG C of constant temperature 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains containing auxiliary agent
Hydrated alumina Q-S2.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
Q-S2 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
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, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 3
Weigh respectively in terms of butt 453 grams of 126 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder be 3.60), and be added 13.21 grams of ammonium dihydrogen phosphates, they are mixed with 3600 grams of deionized waters and is stirred
Mix slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, after closed
It is heated to 160 DEG C of constant temperature 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains containing auxiliary agent
Hydrated alumina Q-S3.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
Q-S3 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
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, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 4
147 grams of 110 grams of 88 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 248 grams of powder, 178 grams of CL-A-600 powder
7.81) they are mixed with 3600 grams of deionized waters, and 51.12 grams of titanium sulfates are added, stirs into slurries；The slurries are shifted
To the volume with stirring be 5 liters stainless steel band polytetrafluoro liner autoclave in, 160 DEG C of constant temperature is heated to after closed 4 hours；
It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain the hydrated alumina Q-S4 containing auxiliary agent.Pass through X-
Diffraction characterizes its crystalline phase, crystallinity and grain size, and the results are shown in Table 1.
Q-S4 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
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, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 5
185 grams of 102 grams of 146 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 450 295 grams of powder, 8 grams of CL-A-600 powder
4.05) they are mixed with 3100 grams of deionized waters, and 20.56 grams of zinc nitrate hexahydrates, 49.12 gram of six nitric hydrate is added
Magnesium and 10.56 grams of ammonium fluorides, stir into slurries；The slurries are transferred to the stainless steel band polytetrafluoro that the volume with stirring is 5 liters
In the autoclave of liner, 60 DEG C of constant temperature is heated to after closed 48 hours；It is down to room temperature and after filtering, filter cake is dry in 120 DEG C
Dry 8 hours, obtain the hydrated alumina Q-S5 containing auxiliary agent.Its crystalline phase, crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.
Q-S5 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
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, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 6
96 grams of 205 grams of 77 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 396 grams of powder, 18 grams of CL-A-600 powder
9.29) they are mixed with 3200 grams of deionized waters, and 14.67 grams of lanthanum nitrate hexahydrates and 15.32 gram of six nitric hydrate is added
Cerium stirs into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters,
100 DEG C of constant temperature is 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, contained
There is the hydrated alumina Q-S6 of auxiliary agent.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, is as a result listed in
In table 1.
Q-S6 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
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, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 7
62 grams of 20 grams of 64 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 18 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 35 grams of CL-B-400 powder, 15 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
(mass ratio of the total amount of the powder of CL-350~600 and the CL powder in terms of butt is 8.10), by them and 3600 grams of deionized waters
Mixing, and 29.76 grams of boric acid are added, stir into slurries；The slurries are transferred to the stainless steel band that the volume with stirring is 5 liters to gather
In the autoclave of tetrafluoro liner, 160 DEG C of constant temperature is heated to after closed 4 hours；It is down to room temperature and after filtering, by filter cake in 120
DEG C dry 8 hours, obtain the hydrated alumina Q-S7 containing auxiliary agent.Its crystalline phase, crystallinity are characterized by X-ray diffraction method
And grain size, the results are shown in Table 1.
Q-S7 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S7 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures its ratio
Surface area and Kong Rong, the results are shown in Table 2.
Embodiment 8
62 grams of 20 grams of 64 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 18 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 35 grams of CL-B-400 powder, 15 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
(mass ratio of the total amount of the powder of CL-350~600 and the CL powder in terms of butt is 8.10), by them and 3600 grams of deionized waters
Mixing adds 85.58 grams of Ludox (the 30 weight % containing silica is purchased from Haiyang Chemical Plant, Qingdao), stirs into slurries；It will
The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, and 160 DEG C are heated to after closed
Constant temperature 4 hours.It is cooled to room temperature, high pressure kettle cover is opened, it is after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains containing helping
The hydrated alumina powder Q-S8 of agent.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, is as a result listed in
In table 1.
By Q-S8 banded extruder (manufacturers：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 in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S8.It is big that its crystalline phase, crystallinity and crystal grain are characterized by X-ray diffraction method
Small, 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 9
62 grams of 20 grams of 64 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 18 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 35 grams of CL-B-400 powder, 15 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
(mass ratio of the total amount of the powder of CL-350~600 and the CL powder in terms of butt is 8.10), by them and 3600 grams of deionized waters
Mixing adds 83.98 gram of eight hydration zirconium oxychloride, stirs 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 is heated to after closed 4 hours.It is cooled to room temperature, by high pressure kettle cover
It opens, it is after filtering, filter cake is 8 hours dry in 120 DEG C, obtain the hydrated alumina powder Q-S9 containing auxiliary agent.It is penetrated by X-
Line diffraction method characterizes its crystalline phase, crystallinity and grain size, and the results are shown in Table 1.
By Q-S9 banded extruder (manufacturers：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 in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S9.It is big that its crystalline phase, crystallinity and crystal grain are characterized by X-ray diffraction method
Small, 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 10
300 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 1.30), they and 3600 grams of deionized waters to be mixed into slurries, and 9.08 grams of di(2-ethylhexyl)phosphates are added
Hydrogen ammonium, stirs into slurries；The slurries are transferred to the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters
In, 200 DEG C, and constant temperature 4 hours under stiring are heated to after closed；Later, it is down to room temperature and after filtering, by filter cake in 120
DEG C dry 8 hours, obtain modified product Q-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.
By 0-S10 banded extruder (manufacturers：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 in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S10.Its crystalline phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Comparative example 1-3 illustrate by conventional method of modifying prepare the modifier of boehmite and/or false boehmite with
And the alumina support being prepared by the modifier.
Comparative example 1
474 grams of the CL-A powder in terms of butt is weighed, it is mixed with 3600 grams of deionized waters, and 10.89 grams of phosphoric acid are added
Ammonium dihydrogen stirs into slurries；The slurries are transferred to the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters
In, 160 DEG C of constant temperature is heated to after closed 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains
Modified hydrated alumina QBF-1.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, is as a result arranged
In table 1.
QBF-1 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support DS1 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures it
Specific surface area and Kong Rong, the results are shown in Table 2.
Comparative example 2
474 grams of CL-A-600 powder are weighed, it is mixed with 3600 grams of deionized waters, and 10.89 grams of ammonium dihydrogen phosphates are added,
Stir into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 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 8 hours dry in 120 DEG C, it obtains modified
Hydrated alumina QBF-2.Its crystalline phase, crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
QBF-2 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support DS2 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measures it
Specific surface area and Kong Rong, the results are shown in Table 2.
Comparative example 3
530 grams of the CL-B powder in terms of butt is weighed, it is mixed with 3600 grams of deionized waters, and 9.08 grams of di(2-ethylhexyl)phosphates are added
Hydrogen ammonium, stirs into slurries；The slurries are transferred to the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters
In, 200 DEG C of constant temperature is 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
Modified hydrated alumina QBF-3.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method,
The results are shown in Table 1.
QBF-3 is extruded into banded extruder (with embodiment 1) to the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar passes through
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support DS3 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 Kong Rong, the results are shown in Table 2.
The crystallinity and grain size of 1 aluminium oxide of table
Wherein, when measuring the crystallinity of false boehmite, using CL-A powder as standard specimen；In the knot for measuring boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When measuring gama-alumina crystallinity, with CL-B-Al2O3For standard specimen.
The specific surface area and Kong Rong of 2 aluminium oxide of table
| 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 | 264 | 0.67 |
| 2 | S2 | 249 | 0.63 |
| 3 | S3 | 225 | 0.62 |
| 4 | S4 | 246 | 0.63 |
| 5 | S5 | 276 | 0.69 |
| 6 | S6 | 268 | 0.67 |
| 7 | S7 | 227 | 0.62 |
| 8 | S8 | 232 | 0.62 |
| 9 | S9 | 255 | 0.64 |
| 10 | S10 | 195 | 0.61 |
| Comparative example 1 | DS1 | 234 | 0.53 |
| Comparative example 2 | DS2 | 175 | 0.60 |
| Comparative example 3 | DS3 | 133 | 0.46 |
Embodiment 11-23 illustrates catalyst provided by the invention and its preparation.
Embodiment 11-20
Respectively with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49 grams of phosphoric acid (mass fraction 85%) and
S1, S2 that 199 milliliters of aqueous solution dipping, 200 grams of embodiment 1-10 of 16.20 grams of citric acids are prepared, S3, S4, S5, S6,
S7, S8, S9 and S10, dip time 2 hours, impregnation product is 4 hours dry in 120 DEG C later, obtain catalyst C1, C2, C3,
C4, C5, C6, C7, C8, C9 and C10.
Embodiment 21
With containing 28.22 grams of MoO3, 1.28 grams of trans- 1,2-cyclohexanediaminetetraacetic acid, 3.56 grams of ethylenediamine tetra-acetic acids, 2.58
What 199 milliliters of dipping embodiments 1 of ammonia spirit of gram malic acid, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates were prepared
S1, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.86 grams of cabaltous nitrate hexahydrates, 17.82 grams of ethylenediamine tetraacetics
199 milliliters of above-mentioned carriers of dipping of ammonia spirit of acetic acid and 3.26 grams of ammonium oxalate, dip time 2 hours, later impregnation product in
120 DEG C of dryings 4 hours, obtain catalyst C11.
Embodiment 22
With containing 28.22 grams of MoO3,0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acids, 1.56 grams of formic acid and 36.23 grams of citric acids
The S1 that is prepared of 199 milliliters of ammonia spirit dipping embodiments 1, impregnation product is 4 hours dry in 120 DEG C later；Then again
With 199 milli of ammonia spirit containing 22.86 grams of cabaltous nitrate hexahydrates, 21.27 grams of ethylenediamine tetra-acetic acids and 1.86 grams of aminotriacetic acids
It rises and impregnates above-mentioned carrier, dip time 2 hours, impregnation product is 4 hours dry in 120 DEG C later, obtains catalyst C12.
Embodiment 23
Prepare with the hydrated alumina Q-S2 powder of 2 equivalent of embodiment, then with 36 grams of Hydrogen Y molecular sieve (Na2O content
0.2%, cell parameter 2.464, relative crystallinity 88%, be purchased from sinopec 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)) be extruded into circumscribed circle diameter be 1.6 millimeters three
Clover shape item, it is 4 hours dry through 120 DEG C, finally 600 are raised to 4 DEG C/min of heating rate in Muffle furnace in air atmosphere
DEG C, then in 600 DEG C of constant temperature 4 hours, obtain alumina support S11.
11200 grams of carrier S is weighed, with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrate, 2.49 grams of phosphoric acid (quality
Score 85%) and 16.20 grams of citric acids 199 milliliters of aqueous solution dipping, dip time 2 hours, impregnation product is in 120 DEG C later
It is 4 hours dry, obtain catalyst C13.
Comparative example 4-7 illustrates reference catalyst and its preparation.
Respectively with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49 grams of phosphoric acid (mass fraction 85%) and
199 milliliters of dippings of aqueous solution 200 grams of carriers DS1, DS2, DS3 and CL-A-Al of 16.20 grams of citric acids2O3, dip time 2 is small
When, impregnation product is 4 hours dry in 120 DEG C later, obtains catalyst D1, D2, D3 and D4.
Catalyst performance evaluation：
The hydrodesulfurization performance that embodiment 11-23 provides the reference catalyst that catalyst and comparative example 4-7 are provided is evaluated,
As a result it is listed in table 3.
Using contain 0.58 weight % of dibenzothiophenes (DBT) n-decane mixed solution as raw material, in high-pressure micro-device
(manufacturer：Beijing petrochemical industry information automation company, model：DADI the hydrodesulfurization activity that catalyst is evaluated on), will be catalyzed
Agent is broken into the particle of a diameter of 40-60 mesh, and the loadings of catalyst are 0.15 gram.
Before formal charging, first catalyst is carried out respectively using the hexamethylene containing 5 weight % carbon disulfide as sulfurized oil pre-
Vulcanization, the condition of presulfurization include：Pressure is 4.14MPa, and temperature is 362 DEG C, and the time is 3.5 hours, sulfurized oil feed rate
For 0.2 ml/min.
After vulcanization, it is 282 DEG C to be cooled to reaction temperature, cuts raw material.Reaction condition includes：Raw material feed rate is
0.2 ml/min, hydrogen partial 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-MASS gas chromatograph-mass spectrometers, the results are shown in Table 1.Wherein, DBT plus
The desulphurizing activated A of hydrogen is calculated as follows：A=ln [100/ (100-X)],
In formula, X is the conversion ratio of DBT
Take the DBT of comparative catalyst D4 hydrodesulfurization activity be 100, then the opposite DBT of other catalyst plus hydrogen take off
Sulphur activity can be represented by the formula：
Relative activity=(AQT/AD4) × 100%,
A in formulaQTFor the activity of other catalyst, AD4For the activity of reference catalyst.
Based on direct desulfurization selectivity S is come by the ratio of both biphenyl and cyclohexyl benzene content in hydrodesulfurization reaction product
It calculates.
It is selectively 100 to take the direct desulfurization of the DBT of comparative catalyst D4, then the opposite DBT's of other catalyst is direct
Desulfuration selectivity can be represented by the formula：
Relatively direct desulfuration selectivity=(SQT/SD4) × 100%.
Table 3
By table 3 the results show that hydrogenation catalyst according to the present invention shows preferable hydrodesulfurization activity and more
High direct desulfurization selectivity.
Claims (21)
1. a kind of hydrogenation catalyst, contain the aluminium oxide shaping carrier, organic compound, at least one selected from the containing adjuvant component
VIII group and at least one metal component selected from group VIB, which is characterized in that the aluminium oxide molding containing adjuvant component carries
Body is obtained by a kind of boehmite of modification containing adjuvant component and/or false boehmite through being molded, roasting, and is contained with described
On the basis of the butt of the boehmite of adjuvant component and/or false boehmite, the matter of the adjuvant component based on the element
Amount score is 0.1%-10%, one kind in III A, IV A, V A, VII A, II A, II B, III B, IV B races of the adjuvant component or
Several, the boehmite containing adjuvant component and/or false boehmite are prepared by method comprising the following steps：
（1）At least one hydrated alumina is roasted, 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）Obtained product of roasting and at least one boehmite and/or false boehmite, group containing auxiliary agent
Compound and the water mixing divided, obtains a kind of mixture；
（3）By step（2）Obtained mixture carries out hydro-thermal process in closed reactor, and hydrothermal conditions include：Temperature
It it is 60 DEG C -250 DEG C, the time is -48 hours 0.5 hour；
（4）By step（3）Obtained product drying；
The organic compound is selected from one or more of the ammonium salt of organic carboxyl acid, organic carboxyl acid.
2. catalyst according to claim 1, which is characterized in that the adjuvant component be selected from fluorine, phosphorus, boron, silicon, magnesium, zinc,
One or more of lanthanum, cerium, titanium and zirconium, with the dry of the boehmite containing adjuvant component and/or false boehmite
On the basis of base, the mass fraction of the adjuvant component based on the element is 0.3%-5%.
3. catalyst according to claim 1, which is characterized in that the step（1）Roasting condition include：Temperature is
300-750 DEG C, the time is 1-24 hours.
4. catalyst according to claim 3, which is characterized in that the step（1）Roasting condition include：Temperature is
350-650 DEG C, the time is 2-10 hours.
5. catalyst according to claim 1, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It it is 60 DEG C to less than 140 DEG C, the time is 0.5-48 hours.
6. catalyst according to claim 5, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It it is 80-120 DEG C, the time is 4-24 hours.
7. catalyst according to claim 1, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
For 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.
8. catalyst according to claim 7, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It it is 150-220 DEG C, the time is 4-24 hours.
9. catalyst according to claim 1, which is characterized in that the step（4) drying temperature is 60 DEG C -180 DEG C,
Drying time is -24 hours 0.5 hour.
10. catalyst according to claim 9, which is characterized in that the step（4) drying temperature is 80 DEG C -150
DEG C, drying time is -12 hours 1 hour.
11. catalyst according to claim 1, which is characterized in that the hydrated alumina is selected from boehmite, vacation
One or more of boehmite, hibbsite.
12. catalyst according to claim 11, which is characterized in that the hibbsite is gibbsite.
13. catalyst according to claim 1, which is characterized in that the step（2）By step（1）Obtained roasting production
In the mixture that object is mixed to get at least one boehmite or false boehmite and water, solid content in mass
For 1%-80%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.1-
20。
14. catalyst according to claim 13, which is characterized in that the step（2）By step（1）Obtained roasting production
In the mixture that object is mixed to get at least one boehmite or false boehmite and water, solid content in mass
For 5%-70%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.2-
12。
15. catalyst according to claim 1, which is characterized in that the group VIII metal component be selected from nickel and/or
The metal component of cobalt, group VIB is selected from molybdenum and/or tungsten, and on the basis of catalyst, the content of the metal component of group VIII is 1-
The content of 10 weight %, metal component of group VIB are 5-40 weight %.
16. catalyst according to claim 15, which is characterized in that on the basis of catalyst, the group VIII metal group
The content divided is 1.5-6 weight %, and the content of metal component of group VIB is 10-35 weight %.
17. catalyst according to claim 1, which is characterized in that on the basis of catalyst, the organic compound contains
Amount is 0.1-30 weight %.
18. catalyst according to claim 17, which is characterized in that the organic carboxyl acid is selected from trans- 1,2- hexamethylenes two
Amine tetraacethyl, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid
One or more of with malic acid, on the basis of catalyst, the content of the organic compound is 1-20 weight %.
19. catalyst according to claim 1, which is characterized in that in the aluminium oxide shaping carrier 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.
20. catalyst according to claim 19, which is characterized in that on the basis of the carrier, the clay and/or point
The mass fraction of son sieve is 1%-20%.
21. 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 the catalyst described in claim 1-20 any one.
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| CN106635139B (en) * | 2017-01-13 | 2019-07-09 | 武汉科林精细化工有限公司 | A kind of application of catalyst in crude benzol and coal based naphtha hydrogenation mixture |
| US11420193B2 (en) * | 2017-07-21 | 2022-08-23 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and organic additive |
| CN110372004B (en) * | 2019-07-29 | 2021-06-29 | 中国石油大学(北京) | Method for regulating and controlling distribution of microscopic aluminum of ZSM-5 molecular sieve and application |
| CN112742404B (en) * | 2019-10-31 | 2023-07-14 | 中国石油化工股份有限公司 | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method |
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| CN1766051A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | High activity medium oil type hydrocracking catalyst and its preparation method |
| CN101722039A (en) * | 2008-10-21 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN103285939A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN104066818A (en) * | 2011-12-09 | 2014-09-24 | 雪佛龙美国公司 | Hydroconversion of renewable feedstocks |
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|---|---|---|---|---|
| CN1766051A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | High activity medium oil type hydrocracking catalyst and its preparation method |
| CN101722039A (en) * | 2008-10-21 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN104066818A (en) * | 2011-12-09 | 2014-09-24 | 雪佛龙美国公司 | Hydroconversion of renewable feedstocks |
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