A kind of preparation method of big pore volume alumina support
Technical field
The invention belongs to field of inorganic material preparing technology, it is related to a kind of preparation method of big pore volume alumina support, more specifically
Say, amorphous alumina and auxiliary agent solid phase are turned brilliant the present invention relates to one kind, are mediated, shaping, dry, roasting is obtained aluminum oxide
The method of carrier.
Background technology
Have that specific surface area is big, pore structure is controllable, heat endurance good due to aluminum oxide, high adsorption capacity the features such as, it is wide
It is general as catalyst, catalyst carrier and adsorbent etc..When aluminum oxide is as catalyst or carrier, its property is to whole catalyst
Performance play very important effect.Typically require that the crystallinity of aluminum oxide should be higher, impurity content should be relatively low, should have suitable
Suitable specific surface area, pore volume and aperture, while also to have certain acidity and acid strength.
As a rule, the aluminum oxide as catalyst and catalyst carrier needs design specific surface area as high as possible, with
Catalytic site and the concentration of activity is set to reach maximum, but in practical ranges, the relation in specific surface area and aperture is opposition
's.Especially in petroleum refining, with the increasingly in poor quality of petroleum resources, there are a large amount of organo-metallic compounds in feedstock oil
And asphalitine, most common of which metal is nickel, vanadium and iron.These metals are highly detrimental to various petroleum refining operations, such as add
Hydrogen cracking, hydrodesulfurization and catalytic cracking.These metals and asphalitine can cause the pore plugging of beds and reduction is urged
The agent life-span.A large amount of metal deposits on catalyst tend to make catalyst poisoning or inactivation.To prevent or slowing down catalyst
Poisoning or inactivation, it is necessary to sufficiently large hole is diffused, but will reduce specific surface area while improving hole.
Research shows, although hole of the diameter less than 6nm can increase the active portion digit of some silica/alumina hydrogenation catalysts
Measure, but these positions can be completely clogged with soot first, cause active reduction.Meanwhile, if being more than 10% total pore volume in catalyst
Hole by aperture more than 60nm (macropore) is occupied, then the mechanical crushing strength and catalysis activity of the catalyst can be reduced.
Therefore, the high-specific surface area, moderate and hydrothermally stable the aluminum oxide of pore size distribution that are suitable for catalyst carrier are prepared as numerous loads
The target of body researcher.
Petroleum refining generally has following three kinds of methods with petrochemical industry alumina support:Most commonly intending thin water aluminium
Stone is raw material, through extruded moulding, drying, roasting, cylinder or bar shaped aluminum oxide is obtained, or increase shaping is made after extruded moulding
Grain operation, is obtained spherical or other shapes aluminum oxide, and the method is most widely used;Second method is that aluminium hydroxide quickly takes off
Amorphous alumina obtained by water is raw material, and shaping, health, drying, the prepared ball-aluminium oxide of roasting, this kind of product are rolled through rotary drum
Product are typically used as adsorbent;Have again and boehmite is exactly prepared as aluminium glue, instilled deep fat post or oil ammonia column through aging
Treatment, dry, roasting are obtained ball-aluminium oxide.
As preparing the most important raw material of alumina support --- the production method of boehmite is broadly divided into Organic Alcohol
Aluminium method and inorganic neutralisation.Organo-aluminium alcoholate method refer to German Condea companies succeed in developing one kind with high-purity aluminium skimmings and higher alcohol
(n-amyl alcohol, n-hexyl alcohol) be raw material production high-quality boehmite, its production include aluminum hydroxide-aluminum oxide-aluminium -ol aluminium-
The cyclic process of aluminium hydroxide.Domestic boehmite production mainly uses inorganic neutralisation, including alkaline process, acid system and double aluminium
Method.Amorphous alumina, as another important source material for preparing alumina support, is as obtained in gibbsite quick burning
Aluminum oxide with ρ-or χ-crystal structure, most significant characteristic is but the activated alumina with high porosity and low cost
With its wide variety of some shortcoming is limited, such as activated alumina it is unstable due to its free energy high, in high response, by
In the fast dewatering method for forming activated alumina, its crystal formation is unbodied.
CN1088397C patents disclose a kind of preparation method of the alumina support for being suitable as heavy-oil hydrogenation catalyst,
A kind of aluminum contained compound solution is contacted with a kind of precipitant solution, the slurries containing aluminium hydroxide are obtained, filtered, wash, done
Dry, crushing, shaping obtain target product.CN1057443A is disclosed and for sour gas to be passed through inclined sodium chlorate solution, then aging,
The method that washing, separation of solid and liquid, drying, shaping prepare alumina support.CN1762579A discloses a kind of big pore volume aluminum oxide
Preparation method, be organic solvent with water, Organic Alcohol or miscible with water the aqueous solution in it is a kind of as solvent, by aluminium salt and
Cyclodextrin adds aqueous slkali to pH value to be more than or equal to 6 in wherein, then through washing, dry, crush, it is prepared by the step such as shaping
Go out alumina support.US3223483 reports amorphous alumina and rolls the method that shaping prepares low sodium ball-aluminium oxide, but should
Ball-aluminium oxide pore volume is typically each relatively low obtained in method.
Existing extruded moulding method consumes a large amount of soda acids firstly the need of prepared boehmite, whole process, produces very
Many high-salt wastewaters, carrier forming process needs to dry twice, that is, preparing the rich diaspore powder of plan need to carry out primary drying, mediate,
Need to carry out redrying after extruded moulding, and pore volume loss of the forming process to powder is larger.Amorphous alumina rolls shaping
Gained alumina support pore volume is smaller, is mainly used in adsorbent, is not suitable for use in needing the oil hydrogenation agent carrier of big pore volume.
The content of the invention:
It is an object of the invention to provide a kind of simplicity it is easy-to-use be particularly well-suited to heavy oil, residual hydrogenation with big pore volume aluminum oxide
The preparation method of carrier.The method reduces dry, pulverizing process during preparing, there is provided a kind of simple to operate, with low cost, product
The preparation method of the alumina support with larger pore volume.
The present invention is a kind of preparation method of alumina support, is carried out according to the following steps:
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina is 5~50
μm, auxiliary agent is selected from the one kind or several in the decomposable alkaline matter in urea, ammonium carbonate, ammonium hydrogen carbonate, methylamine, ethylenediamine
Kind, it is 0.5 to control amorphous alumina and auxiliary agent mass ratio:1~10:1, control the mass ratio of amorphous alumina and water
It is 1:1~10:1;
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, the solid phase turn brilliant reaction time is 1~36h;;
C) solid phase is turned into brilliant product to add water mixing, adds extrusion aid, be kneaded into plastic, oxidation in control plastic
Aluminium and water ratio are 1:5~5:1, extrusion aid addition is the 0.1~20% of quality of alumina;
D) above-mentioned plastic carried out into extruded moulding, drying, be calcined to obtain alumina support.
According to method of the present invention, preferably include:
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina preferably 5~
20 μm, auxiliary agent is selected from one or more in urea, carbonic acid ammonia, ammonium hydrogen carbonate, controls amorphous alumina and the auxiliary agent ratio to be
1:1~5:1, the ratio for controlling amorphous alumina and water is 2:1~5:1;
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, solid phase turn brilliant milled processed equipment used be selected from ball mill,
One or more equipment that superfine mill, Ball-stirring mill etc. are crushed for powder, solid phase turns the crystalline substance reaction time for 6~24h;
C) product is added water mixing, adds extrusion aid, be kneaded into plastic, aluminum oxide and water ratio in control plastic
Example is 2:3~3:2, extrusion aid addition is the 0.5~5% of quality of alumina;
D) drying process of shaping carrier is 80~120 DEG C of dryings 5~24 hours, and roasting process is 450~700 DEG C of roastings
3~8 hours.
According to method of the present invention, it is characterised in that:Extrusion aid is selected from sesbania powder, methylcellulose, hydroxypropyl first
One or more in base cellulose, carboxymethylcellulose calcium, starch, polyvinyl alcohol.
The method of the invention is a kind of to turn brilliant straight forming through solid phase by amorphous alumina and prepare alumina support
Method, whole process is simple and easy to apply, mild condition, energy consumption are low, and obtained alumina support pore volume is big, intensity is high, abrasion are low, is
A kind of method that low cost prepares high-performance alumina support.
Specific embodiment
Embodiment 1
Amorphous alumina, 120g urea and 150g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixture
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 5g sesbania powders, and add water 150g, is mediating
Mediated in machine and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours, 550 DEG C of roastings 5 were small
When obtain cylindrical shaped alumina carrier, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 2
Amorphous alumina, 90g urea and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 12 hours, then take out ground material, add 5g sesbania powders, add water 220g, in kneader
Middle kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, and in 120 DEG C of dryings 8 hours, 550 DEG C were calcined 5 hours
Cylindrical shaped alumina carrier is obtained, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 3
Amorphous alumina, 60g urea and 60g water that 300g particle diameters are 20 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 24 hours, then take out ground material, add 2g sodium carboxymethylcelluloses, add water 180g,
Mediated in kneader and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours, 600 DEG C of roastings
Burning obtains cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 4
Amorphous alumina, 300g ammonium hydrogen carbonate and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then will mixing
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 10g sesbania powders, and add water 350g, is pinching
Mediated in conjunction machine and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 100 DEG C of dryings 12 hours, 600 DEG C of roastings 5
Hour obtains cylindrical shaped alumina carrier, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 5
Amorphous alumina, 200g ammonium hydrogen carbonate and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then will mixing
Material loads superfine mill griding reaction 36 hours, then takes out ground material, adds 15g methylcellulose, adds water
340g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 100 DEG C of dryings 12 hours,
700 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 6
Amorphous alumina, 60g methylamines and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load Ball-stirring mill griding reaction 24 hours, then take out ground material, add 1.5g methylcellulose, add water 150g,
Mediated in kneader and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 80 DEG C of dryings 24 hours, 700 DEG C of roastings
Obtain cylindrical shaped alumina carrier within 3 hours, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 7
Amorphous alumina, 100g ethylenediamines and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then by mixture
Material loads ball mill grinding and reacts 1 hour, then takes out ground material, adds 5g starch, and add water 120g, in kneader
Kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 5 hours, 450 DEG C of roastings 8 hours
To cylindrical shaped alumina carrier, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 8
Amorphous alumina, 100g ethylenediamines and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then will mixing
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 10g hydroxypropyl methyl celluloses, plus
Water 120g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, small in 120 DEG C of dryings 12
When, 500 DEG C of roastings obtain cylindrical shaped alumina carrier in 8 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 9
Amorphous alumina, 300g ammonium hydrogen carbonate and 300g water that 300g particle diameters are 12 μm are sufficiently mixed, then will be mixed
Compound material loads Ball-stirring mill griding reaction 24 hours, then takes out ground material, adds 1.5g polyvinyl alcohol, adds water
148g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours,
550 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 10
Amorphous alumina, 30g urea and 30g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 12 hours, then take out ground material, add 5g sesbania powders, add water 200g, in kneader
Middle kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, and in 120 DEG C of dryings 8 hours, 550 DEG C were calcined 5 hours
Cylindrical shaped alumina carrier is obtained, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
The different embodiment resulting vehicle pore structures of table 1 and intensity index