CN106140314B - A kind of hydrogenation catalyst and its application - Google Patents
A kind of hydrogenation catalyst and its application Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and its application, the catalyst contains aluminium oxide shaping carrier and hydrogenation active metal component containing adjuvant component, it is characterized in that, it is prepared by the method that the catalyst impregnates the carrier using the solution of the compound containing hydrogenation active metal component, before impregnating the carrier with the solution of the compound containing hydrogenation active metal component, include by the carrier in presence of hydrogen with the material haptoreaction containing sulphur or sulfur-containing compound, catalytic condition includes：The volume space velocity of 140 400 DEG C of temperature, 15 megapascal of pressure normal pressure, the material containing sulphur or sulfur-containing compound is 0.1 20h‑1, time of contact is 1 48 hours, and the volume ratio of hydrogen and the material is 100 3000.Compared with prior art, the catalytic performance of present invention offer hydrogenation catalyst is improved.
Description
Technical field
A kind of application the present invention relates to hydrogenation catalyst and its in hydrocarbon oil hydrogenation reaction.
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.
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 aluminium oxide shaping carrier and hydrogenation active metal component containing adjuvant component, institute
State the method preparation that catalyst impregnates the carrier using the solution of the compound containing hydrogenation active metals, which is characterized in that
Before impregnating the carrier with the solution of the compound containing hydrogenation active metals, including by the carrier in presence of hydrogen with containing
There are the material haptoreaction of sulphur or sulfur-containing compound, catalytic condition to include：140-400 DEG C of temperature, pressure normal pressure -15 million
The volume space velocity of pa, the material containing sulphur or sulfur-containing compound is 0.1-20h-1, time of contact be 1-48 hours, hydrogen with it is described
The volume ratio of material is 100-3000.
2. the catalyst according to 1, which is characterized in that the catalytic condition includes：Temperature is 140-400
DEG C, pressure is -10 megapascal of normal pressure, air speed 1-5h-1, time of contact is 2-24 hours, and the volume ratio of hydrogen and the material is
300-1000。
3. the catalyst according to 1, which is characterized in that the material containing sulphur or sulfur-containing compound be pure sulphur or
Sulfur-containing compound, or be sulphur or the mixture of sulfur-containing compound and hydrocarbon ils.
4. the catalyst according to 3, which is characterized in that the material containing sulfur-containing compound is sulphur or sulfur-bearing chemical combination
The mixture of object and hydrocarbon ils, on the basis of the material, the mass fraction of sulphur or sulfur-containing compound is 0.1- in the mixture
15%%, the mass fraction of the hydrocarbon ils is 85-99.9%.
5. the catalyst according to 4, which is characterized in that on the basis of the material, sulphur or sulfur-bearing in the mixture
The mass fraction of compound is 1-6%, and the mass fraction of the hydrocarbon ils is 94-99%.
6. the catalyst according to 1, which is characterized in that the sulfur-containing compound is selected from hydrogen sulfide, CS2, dimethyl two
One or more of thioether, dimethyl sulfide, tert-butyl polysulfide, thiophene and mercaptan.
7. the catalyst according to 1, which is characterized in that the adjuvant component be selected from IIIA, IVA, VA, VIIA, IIA,
One or more of IIB, IIIB, Group IVB, on the basis of the carrier, the quality point of the adjuvant component based on the element
Number is 0.1%-10%.
8. the catalyst according to 7, which is characterized in that the adjuvant component be selected from fluorine, phosphorus, boron, silicon, magnesium, zinc, lanthanum,
One or more of cerium, titanium and zirconium, on the basis of the carrier, the mass fraction of the adjuvant component based on the element is
0.3%-5%.
9. the catalyst according to 1, which is characterized in that the aluminium oxide shaping carrier containing adjuvant component changes for one kind
Property boehmite containing adjuvant component and/or false boehmite obtained after being molded, roasting, it is described containing adjuvant component
Boehmite 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, 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.
10. the catalyst according to 9, 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.
11. the catalyst according to 9, which is characterized in that the hydrothermal conditions of the step (3) include：Temperature 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.
12. the catalyst according to 9, which is characterized in that the hydrothermal conditions of the step (3) include：Temperature is
More than or equal to 140 DEG C to less than equal to 250 DEG C, further preferably 150-220 DEG C, the time is 0.5-48 hours, further excellent
It is selected as 4-24 hours.
13. the catalyst according to 9, which is characterized in that the drying temperature of the step (4) is 60 DEG C -180 DEG C, into
One step is preferably 80 DEG C -150 DEG C, and drying time is -24 hours 0.5 hour, further preferably -12 hours 1 hour.
14. the catalyst according to 9, which is characterized in that the hydrated alumina is selected from boehmite, a false water
One or more of softening aluminium stone, hibbsite.
15. the catalyst according to 14, which is characterized in that the hibbsite is gibbsite.
16. the catalyst according to 9, which is characterized in that product of roasting that the step (2) obtains step (1) with
In the mixture that at least one boehmite or false boehmite and water are mixed to get, 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。
17. the catalyst according to 16, which is characterized in that product of roasting that the step (2) obtains step (1) with
In the mixture that at least one boehmite or false boehmite and water are mixed to get, solid content in mass is
5%-70%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.2-
12。
18. the catalyst according to 1, which is characterized in that the hydrogenation active metal component is selected from least one the
The metal component of group VIII metal component and at least one group VIB, on the basis of catalyst, the group VIII metal component
Content be 1-10 weight %, the content of vib metals component is 5-40 weight %.
19. the catalyst according to 18, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, Section VI B
The metal component of race is selected from molybdenum and/or tungsten, and on the basis of catalyst, the content of the group VIII metal component is 1.5-6 weights
% is measured, the content of vib metals component is 10-35 weight %.
20. the catalyst according to 1, which is characterized in that contain organic matter, the organic compound in the catalyst
One or more of ammonium salt selected from organic carboxyl acid, organic carboxyl acid, on the basis of catalyst, the content of the organic compound
For 0.1-30 weight %.
21. the catalyst according to 20, 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 or more of acid, on the basis of catalyst, the content of the organic compound is 1-20 weight %.
22. 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 1-21 any one.
According to the method provided by the invention, be enough to make the carrier using dipping method introduce hydrogenation active metals it
Before, by the carrier, (material described here is also referred to as oil, example with the material containing sulphur or sulfur-containing compound in presence of hydrogen
If so-called hydrogen to oil volume ratio, oil therein in embodiment refer to just the material containing sulphur or sulfur-containing compound, also referred to as hydrogen and
The volume of material ratio) under the premise of haptoreaction, the present invention to realizing that this catalytic reactor does not specially require,
For example, the haptoreaction is carried out in tubular reactor or in tank reactor.
When the material containing sulphur or sulfur-containing compound is pure sulphur or sulfur-containing compound, preferably to the sulphur or contain
Directly mixed with hydrogen in sulphur compound, formed hydrogen, sulphur or sulfur-containing compound the gaseous mixture, connect again with carrier later
Touch reaction.Such as.By S, H2S、CS2The gaseous mixture that sulfur-containing compound and hydrogen are formed Deng injection hydrogen uses.
It is described when the material containing sulphur or sulfur-containing compound is sulphur or the mixture of sulfur-containing compound and hydrocarbon ils
The preferred boiling range of hydrocarbon ils is kerosene pure hydrocarbon below or distillate, for example, hexamethylene, direct steaming gasoline or straight run kerosene fraction oil.
After described and material haptoreaction containing sulphur or sulfur-containing compound, stops injection and contain sulphur or Containing Sulfur
The material for closing object cools down and obtains and the carrier after the material haptoreaction containing sulphur or sulfur-containing compound.Preferably implementing
Include the step for using inert gas purge after described and material haptoreaction containing sulphur or sulfur-containing compound in mode
Suddenly, for example, hydrogen is switched to inert blowing gas while end and the material haptoreaction containing sulphur or sulfur-containing compound
It sweeps, be cooled to room temperature, obtain and the carrier after the material haptoreaction containing sulphur or sulfur-containing compound.Here, the indifferent gas
Body is preferably nitrogen.
Inventor has found, contacts carrier instead with the material containing sulphur or sulfur-containing compound under conditions of of the present invention
It answers, then hydrogenation active metal component is introduced to the carrier with dipping method, thus obtaining the performance of catalyst is obviously improved.
In the present invention, the aluminium oxide shaping carrier containing adjuvant component can be that any type can be used for preparing plus hydrogen is urged
The aluminium oxide shaping carrier containing adjuvant component of agent.
In a particularly preferred embodiment, the aluminium oxide shaping carrier containing adjuvant component is a kind of modification
Boehmite and/or false boehmite containing adjuvant component obtain after being molded, roasting, the water containing adjuvant component
Softening aluminium stone 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, 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.
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..
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, at least one group VIII and at least one vib metals component are introduced into the carrier
Method is dipping method customary in the art, for example, it may be will contain at least one group VIII and at least one selected from the
Group vib metallic compound is configured to impregnate the method for the carrier after mixed solution；Can will contain at least one Section VIII
Race and at least one method for individually preparing impregnated carrier after solution selected from vib metals compound.Wherein, by containing gold
The adjusting and control for belonging to the concentration, dosage or carrier dosage of the solution of component, can prepare the catalyst of specified content,
This is that those skilled in the art are 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 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, wherein can contain arbitrarily to improving catalyst performance beneficial to organic compound
Object.For example, it is selected from the organic compound of one or more of ammonium salt of organic carboxyl acid, organic carboxyl acid, on the basis of catalyst,
The content of the organic compound is 0.1-30 weight %.The preferably trans- 1,2-cyclohexanediaminetetraacetic acid of the organic carboxyl 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 %.
When containing organic compound in the catalyst, the organic matter can be used together with hydrogenation active metals
The method of dipping introduces carrier, can also be to be drawn using the method for dipping before or after introducing hydrogenation active metals to carrier
Enter.
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.
Compared with existing Hydrobon catalyst, catalyst provided by the invention have preferable hydrodesulfurization activity and
Higher direct desulfurization selectivity, the catalyst are suitable for oil, coal liquefaction fraction oily (for example, gasoline, boat coal, diesel oil etc.)
Unifining process, this catalyst and hydrocracking catalyst are used cooperatively the hydro-upgrading mistake that can be used for heavy distillate
Journey.
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 109, relatively direct desulfurization choosing
Selecting property is up to 116.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 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.
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.
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 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.
The preferably used modified boehmite of embodiment 1-10 declaratives carrier and/or false boehmite,
Preparation 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 in terms of butt are weighed respectively-A-450
(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 in terms of butt are weighed respectively-A-450
(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 in terms of butt are weighed respectively-B-350 18 grams of powder,
20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 35 grams of CL-B-400 powder, CL-C-400 15 grams of powder, 220 grams of CL-A-450 powder,
20 grams of CL-B-450 powder, CL-C-450 10 grams of powder, CL-A-8 grams of 600 150 grams of powder, 22 grams of CL-B-600 powder, CL-C-600 powder (CL-
The total amount of 350~600 powder and the mass ratio of the CL powder in terms of butt are that 8.10), they are mixed with 3600 grams of deionized waters,
And 29.76 grams of boric acid are added, 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, 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 dry in 120 DEG C
Dry 8 hours, obtain the hydrated alumina Q-S7 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-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, CL-C-450 10 grams of powder, CL-A-600 150 grams of 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 in terms of butt are weighed respectively-B-350 18 grams of powder,
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, 220 grams of CL-A-450 powder,
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 Q-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.
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
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 S11 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.
Embodiment 12
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 S12 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.
Embodiment 13
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 S13 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and 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 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.
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 | 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 |
| 11 | S11 | 234 | 0.53 |
| 12 | S12 | 175 | 0.60 |
| 13 | S13 | 133 | 0.46 |
Embodiment 14-27 illustrates the method that carrier of the present invention is contacted with sulfur-containing compound.
Weigh respectively S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12 that embodiment 1-13 is prepared,
S13 and P/CL-A-Al2O3(containing 0.61% phosphorus, specific preparation method is shown in comparative example 1) 200 grams of carrier, is loaded into reactor,
Be passed through the material (also referred herein as oil) containing sulphur or sulfur-containing compound, each embodiment is practical be passed through contain sulphur or sulfur-bearing chemical combination
The material composition of object, haptoreaction condition are listed in table 3.After the haptoreaction, stops injection and contain sulphur or Containing Sulfur
Close the material of object.Hydrogen is switched to nitrogen after reactor is cooled to 150 DEG C, is purged 10 hours；Then it is down to room temperature, is obtained
Carrier R-S1, R-S2, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8, R-S9, R- after being contacted accordingly with sulfur-containing compound
S10, R-S11, R-S12, R-S13 and R-S14.
Embodiment 28-43 illustrates catalyst provided by the invention and its preparation.
Embodiment 28-41
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
R-S1, R that 199 milliliters of dipping embodiment 14-27 of aqueous solution of 16.20 grams of citric acids are prepared-S2、R-S3、R-S4、R-
S5, R-S6, R-S7, R-S8, R-S9, R-S10, R-S11, R-S12, R-S13 and R-S14, dip time 2 hours, impregnate later
Product is 4 hours dry in 120 DEG C, obtain catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13 and
C14。
Embodiment 42
With containing 28.22 grams of MoO3, 1.36 grams of trans- 1,2-cyclohexanediaminetetraacetic acid, 1.58 grams of ethylenediamine tetra-acetic acids, 2.68
What 199 milliliters of dipping embodiments 14 of ammonia spirit of gram malic acid, 1.68 grams of tartaric acid and 2.36 grams of ammonium citrates were prepared
R-S1, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.86 grams of cabaltous nitrate hexahydrates, 12.28 grams of ethylenediamines
199 milliliters of above-mentioned carriers of dipping of ammonia spirit of tetraacethyl and 3.56 grams of ammonium oxalate, dip time 2 hours, later impregnation product
It is 4 hours dry in 120 DEG C, obtain catalyst C15.
Embodiment 43
With containing 28.22 grams of MoO3, 0.18 gram of glyoxalic acid, 1.25 grams of hydroxyacetic acids, 1.58 grams of formic acid, 12.98 grams of citric acids
The R-S1 that 199 milliliters of dipping embodiments 14 of ammonia spirit of ammonium and 10.23 grams of citric acids are prepared, later impregnation product in
120 DEG C of dryings 4 hours；Then again with containing 22.86 grams of cabaltous nitrate hexahydrates, 21.27 grams of ethylenediamine tetra-acetic acids and 1.86 grams of amino
199 milliliters of above-mentioned carriers of dipping of ammonia spirit of triacetic acid, dip time 2 hours, impregnation product is small in 120 DEG C of dryings 4 later
When, obtain catalyst C16.
Comparative example 1 illustrates comparative catalyst and its preparation.
P/CL-A-Al2O3The preparation of (containing 0.61% phosphorus) carrier：Weigh 474 grams of CL-A-Al2O3Carrier, with containing 10.89 grams
475 milliliters of the aqueous solution of ammonium dihydrogen phosphate impregnates 2 hours, 120 DEG C of dryings 4 hours, in air atmosphere 600 DEG C in Muffle furnace
Constant temperature 4 hours.
With containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49 grams of phosphoric acid (mass fraction 85%) and 16.20 grams
199 milliliters of dippings of aqueous solution, 200 grams of P/CL-A-Al of citric acid2O3(containing 0.61% phosphorus) carrier, dip time 2 hours, later
Impregnation product is 4 hours dry in 120 DEG C, obtains catalyst D1.
Catalyst performance evaluation：
Evaluate the hydrodesulfurization performance that embodiment 28-43 provides the comparative catalyst of catalyst and the offer of comparative example 1, knot
Fruit 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 D1 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/AD1) × 100%,
A in formulaQTFor the activity of other catalyst, AD1For 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 D1, then the opposite DBT's of other catalyst is direct
Desulfuration selectivity can be represented by the formula：
Relatively direct desulfuration selectivity=(SQT/SD1) × 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 (26)
1. a kind of hydrogenation catalyst contains aluminium oxide shaping carrier and hydrogenation active metal component containing adjuvant component, feature
Be, the catalyst using the compound containing hydrogenation active metals solution impregnate the carrier method prepare, with containing
Before the solution of the compound of hydrogenation active metals impregnates the carrier, including by the carrier in presence of hydrogen with contain sulphur
Or the material haptoreaction of sulfur-containing compound, catalytic condition include：140-400 DEG C of temperature, -15 megapascal of pressure normal pressure,
The volume space velocity of material containing sulphur or sulfur-containing compound is 0.1-20h-1, time of contact is 1-48 hours, hydrogen and the object
The volume ratio of material is 100-3000.
2. catalyst according to claim 1, which is characterized in that the catalytic condition includes：Temperature is 140-
400 DEG C, pressure is -10 megapascal of normal pressure, air speed 1-5h-1, time of contact is 2-24 hours, the volume ratio of hydrogen and the material
For 300-1000.
3. catalyst according to claim 1, which is characterized in that the material containing sulphur or sulfur-containing compound is pure
Sulphur or sulfur-containing compound, or be sulphur or the mixture of sulfur-containing compound and hydrocarbon ils.
4. catalyst according to claim 3, which is characterized in that the material containing sulphur or sulfur-containing compound be sulphur or
The mixture of sulfur-containing compound and hydrocarbon ils, on the basis of the material, the quality of sulphur or sulfur-containing compound point in the mixture
Number is 0.1-15%, and the mass fraction of the hydrocarbon ils is 85-99.9%.
5. catalyst according to claim 4, which is characterized in that on the basis of the material, in the mixture sulphur or
The mass fraction of sulfur-containing compound is 1-6%, and the mass fraction of the hydrocarbon ils is 94-99%.
6. catalyst according to claim 1, which is characterized in that the sulfur-containing compound is selected from hydrogen sulfide, CS2, dimethyl
One or more of disulfide, dimethyl sulfide, tert-butyl polysulfide, thiophene and mercaptan.
7. catalyst according to claim 1, which is characterized in that the adjuvant component is selected from III A, IV A, V A, VII A, II
A, one or more of II B, III B, IV B races, on the basis of the carrier, the quality point of the adjuvant component based on the element
Number is 0.1%-10%.
8. catalyst according to claim 7, 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, on the basis of the carrier, the mass fraction of the adjuvant component based on the element
For 0.3%-5%.
9. catalyst according to claim 1, which is characterized in that the aluminium oxide shaping carrier containing adjuvant component is one
Kind modified boehmite containing adjuvant component and/or false boehmite obtain after being molded, roasting, the group containing auxiliary agent
The boehmite and/or false boehmite divided is 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.
10. catalyst according to claim 9, which is characterized in that the step（1）Roasting condition include：Temperature is
300-750 DEG C, the time is 1-24 hours.
11. catalyst according to claim 10, which is characterized in that the step（1）Roasting condition include：Temperature is
350-650 DEG C, the time is 2-10 hours.
12. catalyst according to claim 9, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
Degree is 60 DEG C to less than 140 DEG C, and the time is 0.5-48 hours.
13. catalyst according to claim 12, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
Degree is 80-120 DEG C, and the time is 4-24 hours.
14. catalyst according to claim 9, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
Degree is, more than or equal to 140 DEG C to less than equal to 250 DEG C, the time is 0.5-48 hours.
15. catalyst according to claim 14, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
Degree is 150-220 DEG C, and the time is 4-24 hours.
16. catalyst according to claim 9, 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.
17. catalyst according to claim 16, which is characterized in that the step（4) drying temperature is 80 DEG C -150
DEG C, drying time is -12 hours 1 hour.
18. catalyst according to claim 9, which is characterized in that the hydrated alumina is selected from boehmite, vacation
One or more of boehmite, hibbsite.
19. catalyst according to claim 18, which is characterized in that the hibbsite is gibbsite.
20. catalyst according to claim 9, 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。
21. catalyst according to claim 20, 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。
22. catalyst according to claim 1, which is characterized in that the hydrogenation active metal component is selected from least one
The metal component of group VIII metal component and at least one group VIB, on the basis of catalyst, the metal component of group VIII
Content be 1-10 weight %, the content of metal component of group VIB is 5-40 weight %.
23. catalyst according to claim 22, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, the
The metal component of 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 1.5-6 weights
% is measured, the content of metal component of group VIB is 10-35 weight %.
24. catalyst according to claim 1, which is characterized in that contain organic compound in the catalyst, it is described to have
Machine compound is selected from one or more of the ammonium salt of organic carboxyl acid, organic carboxyl acid, on the basis of catalyst, the organic compound
The content of object is 0.1-30 weight %.
25. catalyst according to claim 24, 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 %.
26. 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 1-25 any one.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351110A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Process for presulfurizing hydrocatalyst |
| CN1769377A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
| CN101491765A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrogenation catalyst |
| CN103785402A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst with long service life |
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|---|---|---|---|---|
| WO2006137358A1 (en) * | 2005-06-20 | 2006-12-28 | Chiyoda Corporation | Homogeneous, highly dispersed metal catalyst and process for producing the same |
| CN103079697B (en) * | 2010-06-25 | 2015-07-01 | 吉坤日矿日石能源株式会社 | Hydrodesulfurization catalyst for hydrocarbon oil, production method for same, and hydrorefining method for hydrocarbon oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351110A (en) * | 2000-10-30 | 2002-05-29 | 中国石油化工股份有限公司 | Process for presulfurizing hydrocatalyst |
| CN1769377A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
| CN101491765A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrogenation catalyst |
| CN103785402A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst with long service life |
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