CN106140309A - A kind of hydrogenation catalyst and preparation method and applications - Google Patents
A kind of hydrogenation catalyst and preparation method and applications Download PDFInfo
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- CN106140309A CN106140309A CN201510145499.XA CN201510145499A CN106140309A CN 106140309 A CN106140309 A CN 106140309A CN 201510145499 A CN201510145499 A CN 201510145499A CN 106140309 A CN106140309 A CN 106140309A
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Abstract
A kind of hydrogenation catalyst and application thereof, described catalyst contain carrier and at least one selected from group VIII and at least one is selected from the metal component of vib, it is characterized in that, described carrier is the aluminium oxide article shaped containing anionic surfactant, on the basis of described carrier, the mass fraction of described anionic surfactant is that catalyst described in 0.1%-10% is possibly together with the second Organic substance in addition to anionic surfactant, on the basis of catalyst, described second organic mass fraction is 0.1-30%.Compared with prior art, the present invention provides the performance of catalyst to be improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method and applications.
Background technology
The environmental consciousness day by day strengthened and the strictest environmental regulation force oil refining circle more to focus on cleaning combustion
Material production technology exploitation, how the production super-low sulfur oil product of economical rationality has become oil refining circle current and expected future one
Regularly need one of problem that emphasis solves in the phase.And develop and there is more high activity and selective novel hydrogenation
Catalyst is then to produce one of most economical method of clear gusoline.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of improved hydrogenation catalyst of performance and answers
With.
The present invention relates to herein below:
1. a hydrogenation catalyst, is selected from at least one selected from group VIII with at least one containing carrier
The metal component of vib, it is characterised in that described carrier is containing anionic surfactant
Aluminium oxide article shaped, on the basis of described carrier, the mass fraction of described anion surfactant is
0.1%-10%, described catalyst is possibly together with the second Organic substance in addition to anionic surfactant, to urge
On the basis of agent, described second organic mass fraction is 0.1-30%.
2. according to the catalyst described in 1, it is characterised in that on the basis of described carrier, described anionic
The mass fraction of surfactant is 0.3%-5%, on the basis of catalyst, and described second organic quality
Mark is 1-22%.
3. according to the catalyst described in 1, it is characterised in that described anionic surfactant is selected from carboxylic acid
One or more in salt, sulfuric acid, sulfonate and phosphate ester salt.
4. according to the catalyst described in 3, it is characterised in that described anionic surfactant is selected from oleic acid
One or more in ammonium, enuatrol, ammonium stearate, sodium stearate, dodecylbenzene sodium sulfonate.
5. according to the catalyst described in 1, it is characterised in that containing selected from oxidation in described aluminium oxide article shaped
One or more adjuvant components in silicon, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, with
On the basis of described carrier, the mass fraction of described adjuvant component is less than 10%.
6. according to the catalyst described in 5, it is characterised in that on the basis of described carrier, described adjuvant component
Mass fraction be 0.3%-5%.
7. according to the catalyst described in 1 or 5, it is characterised in that in described aluminium oxide article shaped
Containing clay and/or molecular sieve, on the basis of described carrier, described clay and/or the mass fraction of molecular sieve
It is less than 35%.
8. according to the catalyst described in 7, it is characterised in that on the basis of described carrier, described clay and/or
The mass fraction of molecular sieve is 1%-20%.
9. according to the catalyst described in 1, it is characterised in that described group VIII metal is selected from nickel and/or cobalt, institute
State vib metals selected from molybdenum and/or tungsten, on the basis of described catalyst, described group VIII metal component
Mass fraction be 1-10%, the mass fraction of vib metals component is 5-40%.
10. according to the catalyst described in 9, it is characterised in that on the basis of described catalyst, described group VIII
The mass fraction of metal component is 1.5-6%, and the mass fraction of vib metals component is 10-35%.
11. according to the catalyst described in 1, it is characterised in that described second Organic substance selected from organic carboxyl acid and
One or more of its ammonium salt.
12. according to the catalyst described in 11, it is characterised in that described organic carboxyl acid is selected from trans 1,2-ring
Hexamethylene tetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, second
One or more in aldehydic acid, hydroxyacetic acid, tartaric acid and malic acid.
13. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, are contacted instead with catalyst by hydrocarbon ils
Should, it is characterised in that described catalyst is the catalyst described in aforementioned 1-12 any one
In the present invention, described aluminium oxide can be one or more in γ, η, θ, δ and χ,
It is preferably gama-alumina.Described aluminium oxide has specific surface and the pore volume of conventional alumina, preferential oxidation
The specific surface of aluminum is 150-350 rice2/ gram, more preferably 180-320 rice2/ gram, preferential oxidation aluminum
Pore volume be 0.4-1.1 ml/g, more preferably 0.5-0.9 ml/g.They can be commercially available
Commodity also can be prepared by any one method in prior art.For example, it may be by selected from three aqua oxidations
The mixture of one or more in aluminum, monohydrate alumina and amorphous hydroted alumina is after molding roasting
Prepare.
The molding of described aluminium oxide uses customary way to carry out, as equal in methods such as tabletting, spin, extrusions
Can.When using customary way molding, for guaranteeing being smoothed out to aforesaid material to be formed of molding
(such as, one or more in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina is mixed
Compound) in introduce auxiliary agent be allow, such as when extrusion, can introduce in aforesaid material to be formed
Appropriate peptizer, extrusion aid and water, extrusion molding afterwards.Described peptizer, the kind of extrusion aid and use
It is conventional that amount may each be this area, the most common peptizer can be selected from nitric acid, acetic acid, citric acid,
One or more in formic acid, trichloroacetic acid, hydrochloric acid, malonic acid, described extrusion aid can be selected from sesbania
One or more in powder, methylcellulose, starch, polyvinyl alcohol, PVOH.
In one preferred embodiment, described aluminium oxide article shaped be a kind of modification boehmite and/
Or the gama-alumina that vacation boehmite obtains after molding, roasting.
The method of described modified boehmite and/or false boehmite includes: (1) is by least one oxygen
Changing aluminum hydrate roasting, described roasting condition includes: temperature is 300 DEG C-950 DEG C, and the time is 0.5 little
Time-24 hours；(2) product of roasting that step (1) is obtained and at least one boehmite and/or
False boehmite and water mixing, obtain a kind of mixture；(3) mixture that step (2) is obtained
Carrying out hydrothermal treatment consists in closed reactor, hydrothermal conditions includes: temperature is 60 DEG C-250 DEG C, time
Between be 0.5 hour-48 hours；(4) product that step (3) obtains is dried, obtains a water of modification
Softening aluminium stone and/or false boehmite.
Wherein, the roasting condition of preferred described step (1) including: temperature is 300-750 DEG C, the time
For 1-24 hour.The roasting condition of further preferred described step (1) including: temperature is 350-650
DEG C, the time is 2-10 hour.
The product of roasting that step (1) is obtained by the most described step (2) and at least one boehmite or
In the mixture that false boehmite and water are mixed to get, solid content in mass is 1%-80%, its
In, the mass ratio of described product of roasting and the boehmite counted with butt or false boehmite is as 0.1-
20.The product of roasting that step (1) is obtained by further preferred described step (2) is soft with at least one water
In the mixture that aluminum stone or false boehmite and water are mixed to get, solid content in mass is 5%-
70%, wherein, described product of roasting and the boehmite in terms of butt or the mass ratio of false boehmite
For 0.2-12.
When the water content in described mixture be enough to make described mixture be serosity (such as, in mass
Solid content is less than 35%) time, described step (4) be dried before preferably include filter step.
The hydrothermal conditions of preferred described step (3) including: temperature be 60 DEG C to less than 140 DEG C,
Time is 0.5-48 hour.The hydrothermal conditions of further preferred described step (3) including: temperature
For 80-120 DEG C, the time is 4-24 hour.Or, the hydrothermal treatment consists of preferred described step (3)
Condition includes: temperature is that the time is 0.5-48 hour more than or equal to 140 DEG C to less than or equal to 250 DEG C；Enter
The hydrothermal conditions of the one preferred described step of step (3) including: temperature is 150-220 DEG C, and the time is
4-24 hour.
The baking temperature of the most described step (4) is 60 DEG C-180 DEG C, drying time be 0.5 hour-24 little
Time.The baking temperature of further preferred described step (4) is 80 DEG C-150 DEG C, drying time is 1 hour-
12 hours.
In the present invention, described hydrated alumina is soft selected from Alumina hydrate, false boehmite, a water
One or more in aluminum stone.
Wherein, described Alumina hydrate includes gibbsite (α-Al2O3·3H2O), surge aluminum stone (β1-
Al2O3·3H2And promise diaspore (β O)2-Al2O3·3H2O)。
Described false boehmite is also called boehmite, characterizes with X-ray diffraction, for one at 14.5 °
There is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse in ± 0.5 ° (2 θ).
Described boehmite is also called boehmite, with X-ray diffraction characterize, for one 14.5 ° ±
There is the hydrated alumina (of the strongest, narrow and sharp-pointed (020) crystallographic plane diffraction peak in 0.5 ° (2 θ)
Boehmite 45.8 °, 51.6 ° and 55.2 ° occur respectively corresponding to (131), (220) and
(151) diffraction maximum not available for false boehmite of crystal face).
Inventors of the present invention have surprisingly found that, by boehmite and/or false boehmite with a kind of or
Several through 300 DEG C of-950 DEG C of roastings (heat treatment) 0.5-24 hour, preferably through 300 DEG C of-750 DEG C of roastings
(heat treatment) 1-24 hour, further preferably through 350 DEG C of-650 DEG C of roastings (heat treatment) 2-10 hour
Hydrated alumina and water mixing, obtain a kind of mixture, and by this mixture in hermetic container in
60 DEG C of-250 DEG C of hydrothermal treatment consists 0.5-48 hour, are preferable over 80-220 DEG C of hydrothermal treatment consists 4-24 hour, by
Boehmite and/or the relative crystallinity of false boehmite that this modification obtains improve, and thus through roasting
Burn the aluminium oxide obtained and maintain higher specific surface area and pore volume.
In the present invention, when controlling hydrothermal treatment consists temperature and being more than 140 DEG C, gained modified product is that a water is soft
Aluminum stone；When controlling hydrothermal treatment consists temperature less than 140 DEG C, the crystalline phase of products therefrom keeps one with initiation material
Cause.
In a detailed description of the invention, the crystalline phase preferably making described modified product is consistent with initiation material
The hydrothermal conditions of described step (3) including: temperature be 60 DEG C to less than 140 DEG C, the time is 0.5-
48 hours；The hydrothermal conditions of further preferred described step (3) including: temperature is 80-120
DEG C, the time is 1-24 hour.
In another embodiment, the described step preferably making described modified product be boehmite
Suddenly the hydrothermal conditions of (3) including: temperature is more than or equal to 140 DEG C extremely less than or equal to 250 DEG C, the time
For 0.5-48 hour；The hydrothermal conditions of further preferred described step (3) including: temperature is
150-220 DEG C, the time is 4-24 hour.
In the present invention, described boehmite, false boehmite and gibbsite can be commercially available business
Product, it is also possible to be to use arbitrary prior art to prepare, this is not particularly limited.
Be enough to described hydrated alumina 300 DEG C of-950 DEG C of roastings (heat treatment) 1-24 hour, excellent
Select through 300 DEG C of-750 DEG C of roastings (heat treatment) 1-24 hour, further preferably through 350 DEG C of-650 DEG C of roastings
(heat treatment), under conditions of 2-10 hour, the present invention is to the method for roasting described in step (1) the most especially
Limit.For example, it may be by described hydrated alumina in usual baking oven or roaster in air atmosphere
Under carry out roasting, it is also possible to be in the baking oven or roaster of vacuum-pumping under vacuum or be passed through inertia
Carry out under gas condition.When described roasting is passed through noble gas, described noble gas can be to exist arbitrarily
Be enough to the not oxygen-containing gas gasified under described roasting condition, can be such as selected from nitrogen, argon, helium,
One or more in carbon dioxide and water vapour.
Butt in the present invention refers to: in a certain amount of described hydrated alumina Muffle furnace in air atmosphere
It is raised to 600 DEG C with the heating rate of 4 DEG C/min, then 600 DEG C of constant temperature 4 hours, roasting afterproduct
The percent of the weight ratio of described hydrated alumina, the weight of butt=roasting afterproduct before weight and roasting
Weight × 100% of described hydrated alumina before amount ÷ roasting.
In the present invention, described airtight reactor can be the reaction that can realize described hydro-thermal reaction arbitrarily
Device, such as, autoclave etc., described reaction can be to carry out, also at stirring under static conditions
Under carry out, preferably carry out hydrothermal treatment consists under stirring.
In the present invention, described anion surfactant be can generate after a class is dissociated in water hydrophobicity cloudy from
Sub-compound.Such as, one or more in carboxylate, sulfuric acid, sulfonate and phosphate ester salt.Excellent
Select carboxylate therein, such as, ammonia soap., enuatrol, ammonium stearate, sodium stearate, detergent alkylate
Sodium sulfonate etc..
Be enough to make in described article shaped the anion surface active containing 0.1%-10%, preferably 0.3%-5%
On the premise of agent, the method introducing anion surfactant in described aluminium oxide article shaped is not had by the present invention
Restricted.
In one preferred embodiment, described aluminium oxide article shaped introduces anionic surface activity
The method of agent, including: (1) is with aluminium oxide molding described in the solution impregnation containing anionic surfactant
Thing, the volume of described impregnation liquid is 0.5-20, preferably 1-15 with the ratio of the pore volume of described article shaped；
(2) mixture obtained by dipping carries out heat treatment in closed reactor, heat treatment temperature be room temperature extremely
250 DEG C, preferably 60 DEG C to 220 DEG C, the time is 0.5 hour-48 hours, and preferably 1 hour-36 little
Time；(3) product of drying steps (2), described drying condition includes: temperature is 40 DEG C-250 DEG C,
Being preferably 100 DEG C-180 DEG C, the time is 1 hour-24 hours, preferably 2 hours-18 hours.
Wherein, described room temperature can be the indoor temperature in each season interior throughout the year, generally 5-40 DEG C.
The solvent of described impregnation liquid can be the various solvents that can dissolve described anion surfactant, is preferably
Water, ammonia, ethanol.
On the premise of being enough to make the satisfied requirement of the content of anion surfactant in final described article shaped,
Content and the dipping number of times of the anion surfactant in impregnation liquid are not particularly limited by the present invention.
In the case of being enough to ensure that and carrying out under described heat treatment is at air tight condition, the present invention to described airtight instead
Device is answered to be not particularly limited, common such as autoclave high-pressure reactor etc..
In the present invention, introduce in the method for anion surfactant in described aluminium oxide article shaped, step
(3) purpose being dried is to remove the solvent in impregnation product, on the premise of being enough to realize this purpose,
Described dry method is not limited by the present invention, such as, can be the method for heat drying, it is also possible to be true
The empty method being dried.
In the present invention, in described aluminium oxide article shaped can containing selected from silicon oxide, titanium oxide, magnesium oxide,
One or more adjuvant components in zirconium oxide, thorium oxide, beryllium oxide, on the basis of described carrier, described
The mass fraction of adjuvant component is less than 10%, preferably 0.3%-5%.
When described article shaped contains selected from silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, oxygen
When changing one or more adjuvant components in beryllium, the preparation process in described article shaped includes introducing selected from oxygen
One or more adjuvant components in SiClx, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide
Step, the method for described introducing adjuvant component is conventional method.For example, it may be will contain selected from silicon oxide,
Three hydrations of one or more adjuvant components in titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide
The mixture of one or more in aluminium oxide, monohydrate alumina and amorphous hydroted alumina through molding and roasts
Prepare after burning.Can also be that aluminium oxide and/or its precursor are mixed with the compound containing adjuvant component, it
Obtain by molding, drying and roasting.
In the present invention, described article shaped can contain clay and/or molecular sieve, with described carrier as base
Standard, the mass fraction of described clay and/or molecular sieve is less than 35%, preferably 1%-20%.
When in described article shaped containing clay and/or molecular sieve, wrap in the preparation process of described article shaped
Include introducing clay and/or the step of molecular sieve, the method thing routine side of described introducing clay and/or molecular sieve
Method.Such as, by described clay and/or molecular sieve with described selected from Alumina hydrate, monohydrate alumina
Prepare after molding roasting with the mixture of one or more in amorphous hydroted alumina.
In the present invention, described clay can be selected from Kaolin, halloysite, montmorillonite, kieselguhr, angstrom
One or more in Lip river stone, saponite, rectorite, meerschaum, attapulgite, brucite and bentonite.
Described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.Described zeolite molecular sieve can be hair
Zeolite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite,
ZSM-23 zeolite, ZSM-35 zeolite, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecule
Sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-
One or more in 57 zeolites, faujasite, Beta zeolite and omega zeolite.Described non-zeolite molecular sieve
Can be the one in phosphate aluminium molecular sieve, HTS and SAPO (that is, SAPO) molecular sieve or
Multiple.According to the present invention, described molecular sieve is preferably hydrogen type molecular sieve.Described hydrogen type molecular sieve can be purchased
Obtain, it would however also be possible to employ prepared by conventional method.For example, it is possible to by ammonium ion conventional for sodium form molecular sieve
Exchange process carries out ion exchange and is dried, and forms ammonium type molecular sieve, more fired formation hydrogen type molecular sieve.
Described second organic compound organic carboxyl acid and ammonium salt thereof selected from trans CDTA,
Ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyl second
One or more in acid, tartaric acid and malic acid and ammonium salt thereof.
In the present invention, described hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or add
Hydrogen catalyst for cracking.
The metal component selected from group VIII with selected from vib in described catalyst is conventional selection,
Such as, described group VIII metal component is selected from cobalt and/or nickel, vib metals component selected from molybdenum and/or
Tungsten.
In a specific embodiment, on the basis of described catalyst, described group VIII metal component is (with oxygen
Compound meter, as nickel be NiO, cobalt be CoO) mass fraction be 1-10%, preferably 1.5-6%,
Group vib metal component is (in terms of oxide, if molybdenum is MoO3, tungsten be WO3) mass fraction be 5-40
%, preferably 10-35%.
In the present invention, in described carrier, introduce at least one group VIII and at least one vib gold
Belong to component method be method customary in the art, for example, it may be will containing at least one group VIII with
At least one impregnates the method for described carrier after vib metals compound is configured to mixed solution；
Can be individually will to join selected from vib metals compound with at least one containing at least one group VIII
The method impregnating carrier after solution processed.Wherein, by concentration, consumption or the load of the solution to metallic components
The regulation of body consumption and control, can prepare the described catalyst specifying content, and this is people in the art
Member is readily appreciated by.
According to the present invention, it is dried after described impregnation steps completes, the step such as roasting or not roasting,
The driest, not roasting.The described condition being dried with roasting is all conventional, and such as, baking temperature is
100-300 DEG C, preferably 100-280 DEG C, drying time is 1-12 hour, preferably 2-8 hour；Roasting
Temperature is 350-550 DEG C, preferably 400-500 DEG C, and roasting time is 1-10 hour, and preferably 2-8 is little
Time.
Described group VIII metallic compound one or several in the soluble compound of these metals
Kind, for example, it may be the nitrate of these metals, acetate, carbonate, chloride, solubility complexation
One or more in thing.
Described vib metals compound one or several in the soluble compound of these metals
Kind, for example, it may be in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate
One or more.
The catalyst provided according to the present invention, the most in presence of hydrogen, in 140-370 DEG C
At a temperature of carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can carry out also may be used outside device
In device In-situ sulphiding, the active metal component it loaded is converted into metal sulfide component.
In the present invention, to described hydrotreating reaction condition, there is no particular limitation, preferred reaction condition
Including reaction temperature 200-420 DEG C, more preferably 220-400 DEG C, pressure 2-18 MPa, enter
One step is preferably 2-15 MPa, liquid hourly space velocity (LHSV) 0.3-10 hour-1, more preferably 0.3-5 hour-1,
Hydrogen to oil volume ratio 50-5000, more preferably 50-4000.
The device of described hydrogenation reaction can any be enough to make described raw oil in hydrogenation conditions under with institute
Stating in catalyst catalytic reaction dress device and carry out, such as, described reaction is at fixed bed reactors, mobile
Bed reactor or fluidized bed reactor are carried out.
The catalyst using the present invention to provide can process all kinds of hydrocarbon oil crude material.Such as, described hydrocarbon oil crude material can
To be various heavy mineral oil or artificial oil or their mixed fraction oil, such as selected from crude oil, distillate,
Solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavily depitching
One or more in oil.
Compared with prior art, the present invention provides the hydrogenation activity of catalyst to be improved, particularly by containing the moon
Prepared by the carrier prepared through the hydrated alumina that the method for present invention offer is modified that uses of ionic surface active agent
Catalyst, this modification is particularly evident.
Such as, the aluminium oxide article shaped containing anion surfactant provided by the present invention respectively and routine side
Carrier prepared by method prepares tenor 2.4%NiO and 12%MoO3Hydrobon catalyst C and DC
(reference agent).With containing 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 weight %
The mixed solution of n-decane is raw material, is evaluated the hydrodesulfurization activity of two kinds of catalyst.With catalyst
The activity of DC is 100, and the hydrodesulfurization activity of catalyst C is 112.Result shows, with prior art
The catalyst providing carrier to prepare is compared, the present invention hydrodesulfurization activity providing carrier to prepare catalyst is bright
Aobvious raising.
Detailed description of the invention
Example below will be further illustrated the present invention, but not thereby limiting the invention.
In following example, x-ray fluorescence method is used to be analyzed the content of element each in catalyst surveying
It is fixed that (RIPP132-90, sees: Petrochemical Engineering Analysis method (RIPP test method), and Yang Cui is fixed
Compile, Science Press, 1990,371-375).XRF test before first by catalyst sample at sky
450 DEG C of roastings 6 hours in gas atmosphere.
The mensuration of sample crystalline phase, relative crystallinity and mean grain size is with reference to " solid catalyst Practical Research side
Method " (the big volume of Liu Weiqiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " petrochemical industry is divided
Analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying, Wu Wenhui compile, Science Press,
1990,394-405) the X-ray diffraction method in is carried out.
Modified boehmite that embodiment 1-10 declaratives carrier is used and/or false boehmite,
Its preparation method and the alumina support thus prepared.
The hydrated alumina used in experiment is:
CL-A powder (false boehmite powder), relative relative crystallinity is 100%, grain size
2.9nm, butt 70 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.
CL-B powder (boehmite), relative relative crystallinity is 100%, grain size 5.2nm, dry
Base 78 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company).
CL-C powder (gibbsite (α-Al2O3·3H2O)), relative relative crystallinity is 100%, brilliant
Grain size 156nm, butt 65 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.
Wherein, weigh 10000 grams of CL-A powder, 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 bar that circumscribed circle diameter is 1.6 millimeters.Wet bar
Being dried after 4 hours through 120 DEG C, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain oxygen in air atmosphere
Change alumina supporter CL-A-Al2O3.Its crystalline phase, degree of crystallinity and crystal grain is characterized big by X-ray diffraction method
Little, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and result is listed in table
In 2.
Weigh 10000 grams of CL-B powder, with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry is total
Factory, model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C
Being dried after 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support in air atmosphere
CL-B-Al2O3.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, result arranges
In table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
According to the step (1) in the method for modified boehmite of the present invention and/or false boehmite
The product of roasting obtained is:
CL-A-600: weigh the liter with 4 DEG C/min in 10000 grams of CL-A powder Muffle furnaces in air atmosphere
Temperature speed is raised to 600 DEG C, and within 4 hours, obtains CL-A-600 at 600 DEG C of constant temperature.
CL-A-450: weigh the liter with 3 DEG C/min in 10000 grams of CL-A powder Muffle furnaces in air atmosphere
Temperature speed is raised to 450 DEG C, and within 4 hours, obtains CL-A-450 at 450 DEG C of constant temperature.
CL-A-400: weigh the liter with 5 DEG C/min in 10000 grams of CL-A powder Muffle furnaces in a nitrogen atmosphere
Temperature speed is raised to 400 DEG C, and within 4 hours, obtains CL-A-400 at 400 DEG C of constant temperature.
CL-A-350: weigh the intensification with 3 DEG C/min in 10000 grams of CL-A powder baking ovens in a nitrogen atmosphere
Speed is raised to 350 DEG C, and within 4 hours, obtains CL-A-350 at 350 DEG C of constant temperature.
CL-B-600: weigh the liter with 4 DEG C/min in 10000 grams of CL-B powder Muffle furnaces in air atmosphere
Temperature speed is raised to 600 DEG C, and within 4 hours, obtains CL-B-600 at 600 DEG C of constant temperature.
CL-B-450: weigh the liter with 4 DEG C/min in 10000 grams of CL-B powder Muffle furnaces in air atmosphere
Temperature speed is raised to 450 DEG C, and within 4 hours, obtains CL-B-450 at 450 DEG C of constant temperature.
CL-B-400: weigh the liter with 4 DEG C/min in 10000 grams of CL-B powder Muffle furnaces in air atmosphere
Temperature speed is raised to 400 DEG C, and within 4 hours, obtains CL-B-400 at 400 DEG C of constant temperature.
CL-B-350: weigh the liter with 4 DEG C/min in 10000 grams of CL-B powder Muffle furnaces in air atmosphere
Temperature speed is raised to 350 DEG C, and within 4 hours, obtains CL-B-350 at 350 DEG C of constant temperature.
CL-C-600: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min
Heating rate be raised to 600 DEG C, and within 4 hours, obtain CL-C-600 at 600 DEG C of constant temperature.
CL-C-450: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min
Heating rate be raised to 450 DEG C, and within 6 hours, obtain CL-C-450 at 450 DEG C of constant temperature.
CL-C-400: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min
Heating rate be raised to 400 DEG C, and within 6 hours, obtain CL-C-400 at 400 DEG C of constant temperature.
CL-C-350: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min
Heating rate be raised to 350 DEG C, and within 6 hours, obtain CL-C-350 at 350 DEG C of constant temperature.
Embodiment 1
Weigh 350 grams of CL-A powder in terms of butt, 120 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 0.34 with the mass ratio of the powder of CL-A in terms of butt), they are mixed with 3600 grams of deionized waters and stirs
Mix serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In still, airtight post-heating to 160 DEG C, and under agitation constant temperature 4 hours；Afterwards, it is down to room temperature and passes through
After filter, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S1 being modified.Spread out by X-ray
Shooting method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-
26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C
After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S1 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 measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 2
Weigh 224 grams of CL-A powder in terms of butt, 300 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 1.34 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters
Stir into serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In pressure still, airtight post-heating to 160 DEG C constant temperature 4 hours；Be down to room temperature after filtering, by filter cake in
120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S2 being modified.By X-ray diffraction method
Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S2.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.
Embodiment 3
Weigh 109 grams of CL-A powder in terms of butt, 464 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 4.25 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters
Stir into serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In pressure still, airtight post-heating to 160 DEG C constant temperature 4 hours；Be down to room temperature after filtering, by filter cake in
120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S3 being modified.By X-ray diffraction method
Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
The formed alumina of present invention offer and preparation thereof:
Q-S3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S3.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.
Embodiment 4
Weigh 84 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, CL-A-400 powder respectively
150 grams, 250 grams of CL-A-450 powder, 180 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with
The mass ratio of the CL-A powder in terms of butt is 8.10), they are mixed with 3600 grams of deionized waters and stirs
Mix serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In still, airtight post-heating to 160 DEG C constant temperature 4 hours；Be down to room temperature after filtering, by filter cake in
120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S4 being modified.By X-ray diffraction method
Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S4 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S4.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.
Embodiment 5
Weigh 140 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, CL-A-400 powder respectively
200 grams, 300 grams of CL-A-450 powder, 10 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with
The mass ratio of the CL-A powder in terms of butt is 4.36), they are mixed with 3100 grams of deionized waters and stirs
Mix serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In still, airtight post-heating to 60 DEG C constant temperature 48 hours；Be down to room temperature after filtering, by filter cake in
120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S5 being modified.By X-ray diffraction method
Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S5 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S5.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.
Embodiment 6
Weigh 70 grams of CL-A powder in terms of butt, 200 grams of CL-A-350 powder, CL-A-400 powder respectively
100 grams, 400 grams of CL-A-450 powder, 20 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with
The mass ratio of the CL-A powder in terms of butt is 10.29), they are mixed with 3200 grams of deionized waters and stirs
Mix serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In still, airtight post-heating to 100 DEG C constant temperature 24 hours；Be down to room temperature after filtering, by filter cake in
120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S6 being modified.By X-ray diffraction method
Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S6 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S6.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.
Embodiment 7
Weigh respectively 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, 60 grams of CL-A-350 powder,
20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400 powder 30
Gram, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, CL-C-450 powder
10 grams, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of (CL-of CL-C-600 powder
The total amount of 350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt), by they with 3600 grams
Deionized water is mixed into serosity；The stainless steel band that volume is 5 liters that this serosity is transferred to band stirring gathers
In the autoclave of tetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature and through filtering
After, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S7 being modified.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-
26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C
After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S7 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 measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 8
Weigh respectively 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, 60 grams of CL-A-350 powder,
20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400 powder 30
Gram, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, CL-C-450 powder
10 grams, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of (CL-of CL-C-600 powder
The total amount of 350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt), by they with 3600 grams
Deionized water is mixed into serosity；The stainless steel band that volume is 5 liters that this serosity is transferred to band stirring gathers
In the autoclave of tetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours.After being down to room temperature, by high pressure
Kettle cover is opened, and adds 11.75 grams of ammonium dihydrogen phosphates, room temperature continuation stirring 24 hours, after filtering,
Filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S8 containing auxiliary agent phosphorus being modified.
Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, result is listed in table 1
In.
By Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-
26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C
After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S8 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 measures its specific surface area and pore volume, and the results are shown in Table 2.Use X-fluorescence method to measure to help
The content of agent component, the mass fraction of the described phosphate builder in terms of element is 0.41%.
Embodiment 9
Weigh 224 grams of CL-A powder in terms of butt, 300 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 1.34 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters
Stir into serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In pressure still, airtight post-heating to 160 DEG C constant temperature 4 hours.After being down to room temperature, high pressure kettle cover is opened, adds
Enter 84.51 grams of titanium sulfates, continue stirring 24 hours, then filter.Filter cake is dried 8 through 120 DEG C little
Time, obtain the hydrated alumina Q-S9 containing auxiliary agent titanium being modified.By X-ray diffraction method table
Levying its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S9 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S9.Its crystalline phase, relative crystallinity and crystalline substance is 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 pore volume, and result arranges
In table 2.X-fluorescence method is used to measure the content of adjuvant component, the quality of the described titanium auxiliary agent in terms of element
Mark is 3.12%.
Embodiment 10
Weigh 230 grams of CL-B powder in terms of butt, 320 grams of (CL-A-600 powder of CL-A-450 powder respectively
It is 1.39 with the mass ratio of the powder of CL-B in terms of butt), they are mixed with 3600 grams of deionized waters and stirs
Mix serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In still, airtight post-heating to 200 DEG C, and under agitation constant temperature 4 hours；Afterwards, it is down to room temperature and passes through
After filter, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S10 being modified.Spread out by X-ray
Shooting method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-
26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C
After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S10 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 measures its specific surface area and pore volume, and the results are shown in Table 2.
What the embodiment 11-13 explanation present invention used is prepared boehmite and/or false one by conventional method of modifying
The modifier of boehmite and the alumina support prepared by this modifier.
Embodiment 11
Weigh 470 grams of CL-A powder in terms of butt, by itself and 3600 grams of deionized water mix and blend pulpings
Liquid；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring,
Airtight post-heating was to 160 DEG C of constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried in 120 DEG C
8 hours, obtain the hydrated alumina QBF-1 being modified.It is characterized brilliant by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
QBF-1 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S11.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, result
It is shown in Table 2.
Embodiment 12
Weigh 470 grams of CL-A-600 powder, itself and 3600 grams of deionized waters are mixed into serosity；Should
Serosity transfer to band stirring the stainless steel band polytetrafluoro liner that volume is 5 liters autoclave in, airtight after add
Heat was to 160 DEG C of constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C,
Obtain the hydrated alumina QBF-2 being modified.Its crystalline phase, relatively is characterized by X-ray diffraction method
Degree of crystallinity and grain size, the results are shown in Table 1.
QBF-2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S12.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, result
It is shown in Table 2.
Embodiment 13
Weigh 470 grams of CL-B powder in terms of butt, by itself and 3600 grams of deionized water mix and blend pulpings
Liquid；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring,
Airtight post-heating was to 200 DEG C of constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried in 120 DEG C
8 hours, obtain the hydrated alumina QBF-3 being modified.It is characterized brilliant by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
QBF-3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere
Time, obtain alumina support S13.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, result
It is shown in Table 2.
Table 1
Wherein, when measuring the degree of crystallinity of false boehmite, with CL-A powder as standard specimen；In the crystallization measuring boehmite
When spending, with CL-B powder as standard specimen；When measuring gama-alumina degree of crystallinity, with CL-B-Al2O3For standard specimen.
Table 2
| Embodiment | Aluminium oxide | Specific surface area, m2/g | Pore volume, cm3/g |
| CL-A-Al2O3 | 283 | 0.71 | |
| CL-B-Al2O3 | 201 | 0.51 | |
| 1 | S1 | 255 | 0.66 |
| 2 | S2 | 238 | 0.62 |
| 3 | S3 | 213 | 0.61 |
| 4 | S4 | 236 | 0.62 |
| 5 | S5 | 265 | 0.68 |
| 6 | S6 | 258 | 0.66 |
| 7 | S7 | 216 | 0.60 |
| 8 | S8 | 222 | 0.61 |
| 9 | S9 | 243 | 0.63 |
| 10 | S10 | 185 | 0.60 |
| 11 | S11 | 233 | 0.52 |
| 12 | S12 | 173 | 0.60 |
| 13 | S13 | 131 | 0.45 |
The carrier that the embodiment 14-29 explanation present invention provides, i.e. contains the oxygen of anionic surfactant
Change aluminum article shaped and preparation method thereof.
Embodiment 14
Weigh carrier S 1 200 grams to be placed in autoclave；1.25 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 2 milliliters of mass fraction 25% strong aqua ammonia, 130 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 90 DEG C of constant temperature 24 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S1 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 15
Weigh carrier S 2 200 grams to be placed in autoclave；1.66 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 2 milliliters of mass fraction 25% strong aqua ammonia, 130 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in room temperature place 48 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S2 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 16
Weigh carrier S 3 200 grams to be placed in autoclave；3.58 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 6 milliliters of mass fraction 25% strong aqua ammonia, 130 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 60 DEG C of constant temperature 18 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S3 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 17
Weigh carrier S 4 200 grams to be placed in autoclave；1.08 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 3 milliliters of mass fraction 25% strong aqua ammonia, 140 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 120 DEG C of constant temperature 6 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S4 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 18
Weigh carrier S 5 200 grams to be placed in autoclave；0.77 gram of ammonia soap. is dissolved in ammonia-ethanol solution
200 milliliters (by 2.5 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water,
Mix), be then added in autoclave, airtight after in 160 DEG C of constant temperature 4 hours.By sample after cooling
Product are dried 4 hours in 120 DEG C, obtain aluminium oxide article shaped R-S5 containing anionic surfactant.
In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 19
Weigh carrier S 6 200 grams to be placed in autoclave；4.55 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 8 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 180 DEG C of constant temperature 2 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S6 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 20
Weigh carrier S 7 200 grams to be placed in autoclave；4.93 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 110 DEG C of constant temperature 4 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S7 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 21
Weigh carrier S 8 200 grams to be placed in autoclave；4.31 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 120 DEG C of constant temperature 4 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S8 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 22
Weigh carrier S 9 200 grams to be placed in autoclave；4.46 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 130 DEG C of constant temperature 4 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S9 containing anionic surfactant.Carry
In body, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 23
Weigh carrier S 10 200 grams to be placed in autoclave；1.05 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 80 DEG C of constant temperature 10 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S10 containing anionic surfactant.
In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 24
Weigh carrier S 11 200 grams to be placed in autoclave；1.25 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 90 DEG C of constant temperature 24 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S11 containing anionic surfactant.
In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 25
Weigh carrier S 12 200 grams to be placed in autoclave；1.25 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 90 DEG C of constant temperature 24 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S12 containing anionic surfactant.
In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 26
Weigh carrier S 13 200 grams to be placed in autoclave；1.25 grams of ammonia soap. are dissolved in ammonia-ethanol solution
200 milliliters (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixed
Conjunction forms), be then added in autoclave, airtight after in 90 DEG C of constant temperature 4 hours.By sample after cooling
It is dried 4 hours in 120 DEG C, obtains aluminium oxide article shaped R-S13 containing anionic surfactant.
In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 27
Weigh support C L-A-Al2O3200 grams are placed in autoclave；1.25 grams of ammonia soap. are dissolved in ammonia-second
Alcoholic solution 200 milliliters is (by 12 milliliters of mass fraction 25% strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus
For water, mix), be then added in autoclave, airtight after in 90 DEG C of constant temperature 24 hours.Cooling
After by sample in 120 DEG C be dried 4 hours, obtain the aluminium oxide article shaped containing anionic surfactant
R-S14.In carrier, the mass fraction of anionic surfactant is listed in table 3.
Embodiment 28
Preparation and the modified aluminas hydrate Q-S2 powder of embodiment 2 equivalent, then with 25 grams of silicon dioxide
With banded extruder (manufacturer: south China science and engineering is big after powder (purchased from middle petrochemical industry Chang Ling catalyst branch company) mixing
Subject skill industry head factory, model: F-26 (III)) it is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters
Bar, is dried 4 hours through 120 DEG C, the most in air atmosphere with the heating rate of 4 DEG C/min in Muffle furnace
It is raised to 600 DEG C, then 600 DEG C of constant temperature 4 hours, obtains alumina support S14.
Weigh carrier S 14 200 grams to be placed in autoclave, by 5.25 grams of ammonia soap. and 0.89 gram of dodecyl
Benzene sulfonic acid sodium salt be dissolved in ammonia-ethanol solution 200 milliliters (by 13 milliliters of mass fraction 25% strong aqua ammonia, 150
Milliliter dehydrated alcohol, surplus is water, mixes), be then added in autoclave, airtight after in
100 DEG C of constant temperature 2 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing anionic table
Aluminium oxide article shaped R-S15 of face activating agent.In carrier, the mass fraction of anionic surfactant is listed in
Table 3.
Embodiment 29
The hydrated alumina Q-S2 powder of the modification of preparation and embodiment 2 equivalent, then with 36 grams of Hydrogen Y
Molecular sieve powder (Na2O content 0.2%, cell parameter 2.464, relative crystallinity 88%, purchased from middle petrochemical industry
Chang Ling catalyst branch company) after mixing with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry is total
Factory, model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, it is dried through 120 DEG C
4 hours, the most in air atmosphere Muffle furnace is raised to 600 DEG C with the heating rate of 4 DEG C/min, then
600 DEG C of constant temperature 4 hours, obtain alumina support S15.
Weigh carrier S 15 200 grams to be placed in autoclave, by 6.68 grams of ammonia soap., 1.23 grams of detergent alkylates
Sodium sulfonate and 0.66 gram of enuatrol are dissolved in ammonia-ethanol solution 200 milliliters (by 15 milliliters of mass fractions 25%
Strong aqua ammonia, 150 milliliters of dehydrated alcohol, surplus is water, mixes), it is then added in autoclave,
In 100 DEG C of constant temperature 3 hours after airtight.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing cloudy
Aluminium oxide article shaped R-S16 of ionic surfactant.The quality of anionic surfactant in carrier
Mark is listed in table 3.
The catalyst of embodiment 30-48 explanation present invention offer and preparation thereof.
Embodiment 30-45
Respectively with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of ethylenediamine tetrems
R-S1, R-S2, R-S3, R-that the ammonia spirit 199 milliliters dipping embodiment 14～29 of acid prepares
S4、R-S5、R-S6、R-S7、R-S8、R-S9、R-S10、R-S11、R-S12、R-S13、R-
S14, R-S15 and R-S16, dip time 2 hours, impregnation product is dried 4 hours in 120 DEG C afterwards,
Obtain catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12,
C13, C14, C15 and C16.
Embodiment 46
With containing 34.96 grams of ammonium heptamolybdates, 1.28 grams of trans CDTAs, 3.56 grams of second two
Ammonia spirit 199 milli of amine tetraacethyl, 2.58 grams of malic acids, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates
Rising the R-S1 that dipping embodiment 14 prepares, impregnation product is dried 4 hours in 120 DEG C afterwards；Then
Again with containing 22.62 grams of Nickelous nitrate hexahydrates, 12.27 grams of ethylenediaminetetraacetic acid and the ammonia of 3.26 grams of ammonium oxalate
Solution 199 milliliters impregnates above-mentioned carrier, dip time 2 hours, and impregnation product is dried 4 in 120 DEG C afterwards
Hour, obtain catalyst C17.
Embodiment 47
With containing 34.96 grams of ammonium heptamolybdates, 0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acid, 1.56 grams of formic acid,
The ammonia spirit of 6.98 grams of ammonium citrates and 36.23 grams of citric acids 199 milliliters dipping embodiment 14 prepares
R-S1, afterwards impregnation product in 120 DEG C be dried 4 hours；The most again with containing 22.62 gram of six nitric hydrate
The ammonia spirit 199 milliliters dipping of nickel, 21.27 grams of ethylenediaminetetraacetic acid and 1.86 grams of aminotriacetic acids is above-mentioned
Carrier, dip time 2 hours, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst
C18。
Embodiment 48
Embodiment is impregnated with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates and 22.51 grams of citric acids
14 R-S1 prepared, impregnation product is dried 4 hours in 120 DEG C afterwards；The most again with containing 22.62 grams
The ammonia spirit of Nickelous nitrate hexahydrate and 23.27 grams of ethylenediaminetetraacetic acid 199 milliliters impregnates above-mentioned carrier, leaching
Stain time 2 h, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C19.
Comparative example 1-5 explanation comparative catalyst and preparation thereof.
Comparative example 1
Weigh carrier S 11 200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and
The ammonia spirit of 8.15 grams of ethylenediaminetetraacetic acid 199 milliliters dipping impregnates above-mentioned carrier 2 hours, then exists
120 DEG C are dried 4 hours, obtain catalyst D1.
Comparative example 2
Weigh carrier S 12 200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and
The ammonia spirit of 8.15 grams of ethylenediaminetetraacetic acid 199 milliliters impregnates above-mentioned carrier 2 hours, then at 120 DEG C
It is dried 4 hours, obtains catalyst D2.
Comparative example 3
Weigh carrier S 13 200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and
The ammonia spirit of 8.15 grams of ethylenediaminetetraacetic acid 199 milliliters dipping impregnates above-mentioned carrier 2 hours, then exists
120 DEG C are dried 4 hours, obtain catalyst D3.
Comparative example 4
Weigh support C L-A-Al2O3200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 gram of six hydration nitre
The ammonia spirit 199 milliliters of acid nickel and 8.15 grams of ethylenediaminetetraacetic acid impregnates above-mentioned carrier 2 hours, then
It is dried 4 hours at 120 DEG C, obtains catalyst D4.
Comparative example 5
With the ammonia spirit 199 milliliters dipping containing 34.96 grams of ammonium heptamolybdates and 22.62 grams of Nickelous nitrate hexahydrates
The R-S1 that embodiment 14 prepares 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst
D5。
Catalyst performance evaluation
The hydrogenation evaluating the comparative catalyst that embodiment 30-48 provides catalyst and comparative example 1-5 to provide takes off
Sulfur performance, result is listed in table 3.
Evaluating catalyst with containing 4, the positive last of the ten Heavenly stems of 6--dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 weight %
The mixed solution of alkane is raw material, in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation is public
Department, model: DADI) the upper hydrodesulfurization activity evaluating catalyst, catalyst breakage is become a diameter of
The granule of 40-60 mesh, the loadings of catalyst is 0.15 gram.Before formal charging, first with containing 6 weight %
The hexamethylene of Carbon bisulfide is that sulfurized oil carries out presulfurization to catalyst respectively, and the condition of presulfurization includes: pressure
Power is 4.14MPa, and temperature is 362 DEG C, and the time is 3.5 hours, sulfurized oil feed rate is 0.2 milliliter/
Minute.After sulfuration terminates, being cooled to reaction temperature is 280 DEG C, cuts raw material.Reaction condition includes: former
Material feed rate is 0.2 ml/min, and pressure is 4.14MPa, and hydrogen to oil volume ratio is 900.React 3 little
Sample in high-pressure separator exit time after.Gained sample Agilent6890N gas chromatograph is carried out point
Analysis.Wherein, the hydrodesulfurization activity A of 4,6-DMDBT is calculated as follows:
A=ln [100/ (100-X)],
In formula, X is 4, and (circular of X sees " catalysis to the desulfurization degree of 6-DMDBT
Report ", 2002,23 (3): 271-275).
Taking the 4 of comparative catalyst D1, the hydrodesulfurization activity of 6-DMDBT is 100, then other catalyst
Relative 4, the hydrodesulfurization activity of 6-DMDBT can be represented by the formula:
Relative activity=(AQT/AD1) × 100%, A in formulaQTFor the activity of other catalyst, AD1It is catalyzed for reference
The activity of agent.
Table 3
Shown by the result of table 3, all show higher hydrodesulfurization according to the hydrogenation catalyst of the present invention and live
Property.
Claims (13)
1. a hydrogenation catalyst, is selected from at least one selected from group VIII with at least one containing carrier
The metal component of vib, it is characterised in that described carrier is containing anionic surfactant
Aluminium oxide article shaped, on the basis of described carrier, the mass fraction of described anion surfactant is
0.1%-10%, described catalyst is possibly together with the second Organic substance in addition to anionic surfactant, to urge
On the basis of agent, described second organic mass fraction is 0.1-30%.
Catalyst the most according to claim 1, it is characterised in that on the basis of described carrier, described
The mass fraction of anionic surfactant is 0.3%-5%, on the basis of catalyst, described second organic
The mass fraction of thing is 1-22%.
Catalyst the most according to claim 1, it is characterised in that described anionic surfactant
One or more in carboxylate, sulfuric acid, sulfonate and phosphate ester salt.
Catalyst the most according to claim 3, it is characterised in that described anionic surfactant
One or several in ammonia soap., enuatrol, ammonium stearate, sodium stearate, dodecylbenzene sodium sulfonate
Kind.
Catalyst the most according to claim 1, it is characterised in that contain in described aluminium oxide article shaped
One or more auxiliary agents in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide
Component, on the basis of described carrier, the mass fraction of described adjuvant component is less than 10%.
Catalyst the most according to claim 5, it is characterised in that on the basis of described carrier, described
The mass fraction of adjuvant component is 0.3%-5%.
Catalyst the most according to claim 1 or 5, it is characterised in that in described aluminium oxide article shaped
Containing clay and/or molecular sieve, on the basis of described carrier, described clay and/or the mass fraction of molecular sieve
It is less than 35%.
Catalyst the most according to claim 7, it is characterised in that on the basis of described carrier, described
The mass fraction of clay and/or molecular sieve is 1%-20%.
Catalyst the most according to claim 1, it is characterised in that described group VIII metal selected from nickel and/
Or cobalt, described vib metals is selected from molybdenum and/or tungsten, on the basis of described catalyst, described group VIII
The mass fraction of metal component is 1-10%, and the mass fraction of vib metals component is 5-40%.
Catalyst the most according to claim 9, it is characterised in that on the basis of described catalyst, institute
The mass fraction stating group VIII metal component is 1.5-6%, and the mass fraction of vib metals component is
10-35%.
11. catalyst according to claim 1, it is characterised in that described second Organic substance is selected from having
One or more of machine carboxylic acid and ammonium salt thereof.
12. catalyst according to claim 11, it is characterised in that described organic carboxyl acid is selected from trans
CDTA, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid,
One or more in formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid.
13. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, are contacted instead with catalyst by hydrocarbon ils
Should, it is characterised in that described catalyst is the catalyst described in claim 1-12 any one.
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| CN108126752A (en) * | 2017-11-16 | 2018-06-08 | 福州大学 | A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst and its preparation method and application |
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