CN102451767B - Method for preparing alumina carrier - Google Patents
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Abstract
The invention discloses a method for preparing an alumina carrier. The method comprises the following steps of: drying nanometer aluminum hydroxide gel prepared by a molten salt supersolubility micelle method, extracting by using an organic solvent, drying, and forming to prepare the alumina carrier. In the method, the nanometer aluminum hydroxide gel is extracted by the organic solvent, so that a surfactant and a hydrocarbon component can be removed from the gel, the volume of nanometer self-assembled particles is greatly reduced, the basic form is unchanged, the sizes of pore channels formed in a natural accumulating mode are mainly concentrated in the range of 30 to 100nm, and the proportion of macropores which are formed by the surfactant and the hydrocarbon component in a free mode and have the size of more than 100nm and even more than 1,000nm is small; and the mechanical strength of the carrier obtained after forming can be improved. The alumina carrier can be used in the catalytic reaction of a macromolecular reactant or product, particularly the residue oil hydrotreatment process.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, the preparation method of the macropore alumina supporter of especially suitable residual hydrocracking.
Background technology
, degradation heavy along with the change day by day of oil are brought increasing difficulty to PETROLEUM PROCESSING.Meanwhile, people's environmental consciousness constantly strengthens, and environmental regulation is also more and more stricter, to NO in the motor vehicles discharging waste gas
x, SO
xAnd the restriction of arene content is harsher.
At present, hydrotreatment remains the most important means of production high-quality, environmental friendliness oil product.The core of hydrotreatment technology is catalyst, and the key of the performance of the carrier hydrotreating catalyst that to be preparation property good.For the heavy ends (for example VGO, especially residual oil) of oil, the big young pathbreaker of the aperture of carrier and pore volume directly influences the performance of catalyst activity.
Through hole is very important to petroleum catalyst, and particularly the big molecule of residual oil needs big through hole to carry out the deposition of metal, makes catalyst reach maximum appearance metal ability, improves the life cycle of catalyst.The molecule that contains metal in the residual oil is to exist with colloid and the big molecule of asphalitine, and all about 2000, the micelle of formation is about 10nm for molecular weight.Reactant is conducive to diffusion and reaction with the channel diameter ratio most at 2～6 times, and it is the most effective ducts that the residual oil of 10～100nm is deviate from metal impurities.Residuum hydrogenating and metal-eliminating catalyst begins to inefficacy from running, and keeping the through hole of enough 10nm～100nm to make the big molecular diffusion of residual oil and metal deposition from the surface to the center is the necessary condition of long-term operation.Particularly be difficult to prepare the duct at the alumina support of 30-100nm, and this duct scope is the diffusion that is conducive to very much the asphalitine micelle.
The employed carrier material of catalyst for hydrotreatment of residual oil is generally macroporous aluminium oxide and modified product thereof.The preparation method that macroporous aluminium oxide is commonly used has: physics port-creating method, high-temperature roasting method and pH value swing method.The shortcoming of physics port-creating method is that the duct is inhomogeneous, still has the shortcoming of easy obstruction.The precursor of physics expanding agent such as usefulness such as US4448896, US4102822 carbon black, starch and activated alumina or aluminium oxide mixes the aperture of pinching to enlarge alumina support, the consumption of physics expanding agent is more than the aluminium oxide 10wt%, said method is to add the physics expanding agent in the aluminium oxide precursor, and the consumption of expanding agent is big, cause the pore size distribution disperse of aluminium oxide, big bore portion can not form continuous through hole, and the duct is the ink bottle type, the aperture is less, and intensity is relatively poor.
CN1184078A discloses a kind of preparation method of alumina support.The aluminium hydroxide that this method adopts and stream becomes the glue generation utilizes pH value swing method to make aluminium hydroxide as crystal seed then, and again through extruded moulding, the pore volume that can obtain pore diameter range 10～30nm or 20～60nm accounts for the aluminium oxide of total pore volume more than 70%.During the moulding of pH swing method aluminium oxide, influencing the intensity of carrier and the factor of pore size has two, i.e. peptization acid and pressure, peptization subacidity or pressure all will cause intensity to reduce inadequately, and aperture and pore volume are diminished.The duct is very big between the alumina powder jointed particle of pH swing method, foot comes from that pH swing causes, taken out the duct of a lot of 20～60nm between particle, but during with sour peptization, will be by molten disconnected between particle, under pressure, the duct will be constructed again, the aperture in duct and pore volume can sharply diminish, so very big contradiction is arranged between pore volume and the intensity.
CN1068975A discloses the preparation method of a kind of low-density, large pore volume, high-strength alumina carrier, is the aluminium colloidal sol that obtains with acid treatment, adds gelling agent, obtains through the method for forming oil column, and specific surface is 120～280m
2/ g, bulk density are 0.18～0.35g/cm
3, pore volume is 1.5～2.0cm
3/ g, average pore size is 30～60nm, crushing strength is 0.5～3.0kgf/ grain, as the dehydrogenation of long-chain alkane catalyst.This method is that to add hexamethylenetetramine in the aluminium colloidal sol be gelling agent, this gelling agent has formed hole and window in aluminium colloidal sol, there is aluminium colloidal sol to intercept between hole and the hole, it is theoretical that the arrangement in hole meets the ball dress, between the adjacent hole by the window intercommunication, the duct that this ball dress accumulation mode forms is ink bottle type structure, and the aperture is less, is unfavorable for macromolecular diffusion.Drawbacks such as on the other hand, forming oil column has operating condition abominable, and production efficiency is low.
" the large pore volume meso-porous alumina is synthesized in the nanometer self assembly " (" Chinese science B collects " 420-430 page or leaf) is the gel aluminum hydroxide that adopts super solubilising micelle method preparation, in the dried glue of washing and dry gained, contain a large amount of surfactants and hydrocarbon component, in forming process, there are part surface activating agent and hydrocarbon component to leave nanometer self assembly particle, assemble and form organic matter, caused the distribution of duct wide region, make the large pore volume meso-porous alumina form nanometer to the duct of micron order different frames structure, pore size distribution is not concentrated.And, after the moulding, part surface activating agent and hydrocarbon component are still stayed in the nanometer self assembly particle, make the shared volume of particle bigger, in roasting process, though because surfactant and removing of hydrocarbon component can form big duct and pore volume, although have high appearance metal ability, can influence the mechanical strength of alumina support.
Summary of the invention
At weak point of the prior art, the invention provides the preparation method of the alumina support of a kind of mechanical strength height, pore distribution concentration, suitable big molecular diffusion.
The preparation method of alumina support of the present invention comprises the steps:
(1) adopt the super solubilising micelle of fused salt legal system to be equipped with the nano-aluminum hydroxide gel,
(2) the nano-aluminum hydroxide gel of step (1) gained after drying,
(3) the nano-aluminum hydroxide xerogel of usefulness organic solvent extraction steps (2) gained,
(4) with the nano-aluminum hydroxide drying behind the solvent extraction, obtain nano-aluminum hydroxide;
(5) with the nano-aluminum hydroxide moulding of step (4) gained, drying and roasting obtain alumina support.
The described organic solvent of step (3) is one or more in gasoline, diesel oil, benzinum, toluene, dimethylbenzene, normal heptane and the cyclohexane.The condition of described solvent extraction is as follows: described nano-aluminum hydroxide xerogel is 1: 1～5 with the volume of organic solvent ratio, 50～100 ℃ of temperature, 1～10 hour extracting time, extracting number of times 1～3 time, normal pressure.
The described drying condition of step (2) is as follows: 100～130 ℃ of baking temperatures, 1～30 hour drying time.
The described drying condition of step (4) was as follows: 100～130 ℃ of dryings 1～30 hour.
Step of the present invention (5), the drying condition after the described moulding is as follows: carried out drying 1～30 hour under 100～130 ℃ of temperature; Described roasting can be adopted a conventional one-step baking method, condition was as follows: 180～1200 ℃ of roastings 4～80 hours, programming rate is 0.1～5.0 ℃/min, preferably divide one-step baking, condition was as follows: 180～300 ℃ of roasting temperatures 1～10 hour, 500～1200 ℃ of roastings 2～60 hours, programming rate was 1～5 ℃/min.
The super solubilising micelle of the described employing fused salt of step (1) legal system is equipped with the process of nano-aluminum hydroxide gel, and is such as the CN200510046481.0 disclosed method, specific as follows:
A, hydrocarbon component and VB value are mixed less than 1 surfactant;
B, nano-aluminum hydroxide gel are made by following a kind of method at least:
Method one: the inorganic aluminate of fusion slowly joins in the mixture of steps A gained, is mixed to form even colloid; Add precipitating reagent then, under 50～120 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method two: the inorganic aluminate of fusion is slowly added in the mixture of steps A gained, be mixed to and form even colloid; In confined conditions, below the ammonia critical-temperature, be generally the critical-temperature of 30 ℃～ammonia, add precipitating reagent liquefied ammonia, under 30～200 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method three: use precipitating reagent and inorganic aluminate to mix the back heating and melting, slowly join in the mixture of steps A gained, be mixed to and form even colloid; Under airtight condition, resulting mixture is carried out homogeneous precipitation under 70～200 ℃ of temperature, 1～10 hour reaction time, aging then, obtain the nano-aluminum hydroxide gel;
Weight with the resulting mixture of step B is benchmark, inorganic aluminate (butt), precipitating reagent and water consumption are 60.0wt%～93.0wt%, be preferably 75.0wt%～92.0wt%, the mol ratio of water and aluminium atom is 3～15: 1, be preferably 3～10: 1, the mol ratio of aluminium atom and precipitating reagent is 1: 0.9～5, be preferably 1: 1.2～and 3; The consumption of surfactant is 0.1wt%～15.0wt%, better is 0.5wt%～12.0wt%; The consumption of hydrocarbon component is 6.9wt%～32.0wt%, better is 7.5wt%～24.5wt%; Wherein water can add with the crystallization water and/or free water form in steps A and/or step B.
Among the present invention, in order to obtain purer aluminium oxide, also the weight concentration that can wash the nano-aluminum hydroxide of step (1) gained with water Na ion and Fe ion is all below 0.5%, and water wherein preferably adopts distilled water or deionized water.
The present invention also can add auxiliary agent such as in silicon, titanium, zirconium, magnesium, phosphorus, boron, lanthanum, iron, manganese, the calcium etc. one or more in the alumina support preparation process, the addition of described auxiliary agent can be determined according to actual needs.The adding mode of this auxiliary agent can add before nano-aluminum hydroxide becomes glue, introduce such as adopting the super solubilising micelle of fused salt method, it is the CN200510046480.6 disclosed method, also can after becoming glue, the mode with making beating add, also can before moulding, introduce with kneading method, also can after making alumina support, adopt infusion process to introduce.
Forming method of the present invention can adopt the extruded moulding method.In carrying alumina of the present invention is body formed, needs according to practical application and preparation process, can add peptizing agent, water and cosolvent, detailed process is as follows: nano-aluminum hydroxide, peptizing agent, water and cosolvent that the inventive method is obtained mix, and this process can adopt conventional charging sequence, preferably peptizing agent, water and cosolvent is mixed, be added in the nano-aluminum hydroxide then, stir, mix at batch mixer, moulding in banded extruder then.Described batch mixer can be kneader or roller.In the described extrusion process, controlled pressure is at 10～50MPa.Described peptizing agent can be in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and the sulfuric acid one or more, consumption is 1%～15% (mass fraction) of nano-aluminum hydroxide weight, described water preferably adopts deionized water, consumption is 5%～100% (mass fraction) of nano-aluminum hydroxide weight, preferred 20%～70%.Peptization course also needs to add cosolvent, and cosolvent is one or more in methyl alcohol, ethanol and the propyl alcohol, and consumption is 1%～15% (mass fraction) of nano-aluminum hydroxide weight.
The present invention is in the extruded moulding method, can also add in other the aluminium hydroxide, molecular sieve, adhesive etc. one or more, the aluminium hydroxide that described other aluminium hydroxide can adopt any method to obtain, especially has large pore volume, wide-aperture aluminium hydroxide, the aluminium hydroxide that the nano-aluminum hydroxide gel that obtains such as the super solubilising micelle of fused salt method obtains is after drying specifically seen the aluminium hydroxide that the CN200510046481.0 disclosed method obtains.
The present invention is in the extruded moulding method, can also add adhesive, earlier nano-aluminum hydroxide be mixed with adhesive, perhaps earlier nano-aluminum hydroxide, other aluminium hydroxide be mixed with adhesive, the mixture that adds peptizing agent, water and cosolvent then, extruded moulding again.Described adhesive can adopt one or more in the conventional aluminium oxide as adhesive, titanium oxide, the silica.
The present invention can also add extrusion aid in the extruded moulding method, described extrusion aid is the sesbania powder.
The said porosity of the present invention is the porosity of the particle inner duct that records with mercury injection method.
The prepared alumina support of the inventive method suits especially as catalyst for hydrotreatment of residual oil, the method of alumina support load hydrogenation active metals wherein, any method that can adopt prior art to provide, such as kneading method, infusion process, also can adopt the super solubilising micelle of fused salt legal system to be equipped with in the aluminium hydroxide process and introduce reactive metal.
Nano oxidized alumina supporter of the present invention be nano-aluminum hydroxide gel that super solubilising micelle method is obtained after drying, use organic solvent washing, more after drying, moulding preparation and getting.Owing to contain a large amount of surfactants and organic hydrocarbon in the nano-aluminum hydroxide gel of super solubilising micelle method preparation, in the nano-aluminum hydroxide gel, can reach 50wt%, after the organic solvent extracting, removed this part organic matter, the volume of nanometer self assembly particle is dwindled greatly, and grown form is constant, the duct distribution that forms with natural stacked form mainly concentrates on 30-100nm, by surfactant with more than the free 100nm that forms of hydrocarbon component, or even the macropore proportion more than the 1000nm is very little.And, since surfactant and hydrocarbon component remove the mechanical strength that is conducive to improve gained carrier after the moulding.
Alumina support of the present invention can be used for containing in the catalytic reaction of macromolecular reaction thing or product, refining such as residual hydrogenation, macromolecular polymerization reaction, reactions such as big molecule and high molecular hydrogenation reaction, dehydrogenation reaction, oxidation reaction, aromatisation, isomerization, alkylation, reformation catalysis, etherificate.The high diffusion of the penetrability of carrier of the present invention can make big molecule and macromolecule be diffused into the reaction position easily in the duct, and the macromolecule that forms is diffused out outside the caltalyst.
Description of drawings
Fig. 1 is ESEM (SEM) figure of Comparative Examples 1 alumina support;
Fig. 2 is the SEM figure of embodiment 1 gained alumina support;
Fig. 3 is the pore size distribution figure of Comparative Examples 1 gained alumina support;
Fig. 4 is the pore size distribution figure of embodiment 1 gained alumina support.
The specific embodiment
Pore volume among the present invention, specific surface, average pore size, pore size distribution, porosity adopt mercury injection method to record.Crushing strength adopts intensity meter to measure.Wt% is mass fraction.
Under stirring condition, 375g nine water aluminum nitrates and 90g urea are mixed and heated to 100 ℃, be added in the mixture of the 150HVI neutral oil of 32g polyisobutene maleic acid triethanolamine ester and 88g under the equal temperature condition, form super solubilising micelle, 100 ℃ of reactions 3 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours.Under the normal pressure, with 70 ℃ of diesel oil extractings, the volume ratio of diesel oil and nano-aluminum hydroxide xerogel is 2: 1, and 5 hours extracting time, the extracting number of times is three times, filters then, 100 ℃ of dryings 5 hours, obtains nano-aluminum hydroxide AH1.
100g nano-aluminum hydroxide AH1, the rare nitric acid of 5g (mass concentration 17%), 60g water are mixed, mix at batch mixer, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support A1 of the present invention.
Comparative Examples 1
Under stirring condition, 375g nine water aluminum nitrates and 90g urea are mixed and heated to 100 ℃, be added in the mixture of the 150HVI neutral oil of 32g polyisobutene maleic acid triethanolamine ester and 88g under the equal temperature condition, form super solubilising micelle, 100 ℃ of reactions 3 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours, obtain nano-aluminum hydroxide DAH1.
With 100g nano-aluminum hydroxide DAH1,30g binding agent boehmite, the rare nitric acid of 6.5g (mass concentration 17%), 70g water mix, mix at batch mixer, and moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support DA1.
Embodiment 2
Under stirring condition, 548g nine water aluminum nitrates and 132g urea are mixed and heated to 70 ℃, be added in the mixture of the 150HVI neutral oil of 120g polyisobutene maleic acid triethanolamine ester and 200g under the equal temperature condition, form super solubilising micelle, 150 ℃ of reactions 8 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours.Under the normal pressure, with 70 ℃ of dimethylbenzene extractings, the volume ratio of dimethylbenzene and nano-aluminum hydroxide xerogel is 3: 1, and 3 hours extracting time, the extracting number of times is three times, filter then, and 100 ℃ of dryings 5 hours, the nano-aluminum hydroxide AH2 that obtains.
100g nano-aluminum hydroxide AH2 and binding agent boehmite were mixed by weight 9: 1; The rare nitric acid of 2.4g (mass concentration 17%), 75g water are mixed, be added to then in the mixture of nano-aluminum hydroxide and binding agent, stir, mix at batch mixer, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support A2 of the present invention.
Comparative Examples 2
Under stirring condition, 548g nine water aluminum nitrates and 132g urea are mixed and heated to 70 ℃, be added in the mixture of the 150HVI neutral oil of 120g polyisobutene maleic acid triethanolamine ester and 200g under the equal temperature condition, form super solubilising micelle, 150 ℃ of reactions 8 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours, the nano-aluminum hydroxide DAH2 that obtains.
100g nano-aluminum hydroxide DAH2 and binding agent boehmite were mixed by weight 9: 1; The rare nitric acid of 2.4g (mass concentration 17%), 75g water are mixed, be added to then in the mixture of nano-aluminum hydroxide and binding agent, stir, mix at batch mixer, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support DA2.
Embodiment 3
Under stirring condition, 548g nine water aluminum nitrates and 170g urea are mixed and heated to 70 ℃, be added in the mixture of the 150HVI neutral oil of 25g polyisobutene maleic acid triethanolamine ester and 95g under the equal temperature condition, form super solubilising micelle, 150 ℃ of reactions 8 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours.Under the normal pressure, with 50 ℃ of benzinum extractings, the volume ratio of benzinum and nano-aluminum hydroxide xerogel is 1: 1, and 8 hours extracting time, the extracting number of times is three times, filter then, and 100 ℃ of dryings 5 hours, the nano-aluminum hydroxide AH3 that obtains.
100g nano-aluminum hydroxide AH3 and Comparative Examples 1 DAH1 were mixed by weight 3: 1; The rare nitric acid of 2.4g (mass concentration 17%), 75g water are mixed, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support A3 of the present invention.
Comparative Examples 3
Under stirring condition, 548g nine water aluminum nitrates and 170g urea are mixed and heated to 70 ℃, be added in the mixture of the 150HVI neutral oil of 25g polyisobutene maleic acid triethanolamine ester and 95g under the equal temperature condition, form super solubilising micelle, 150 ℃ of reactions 8 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, through 120 ℃ of dryings 10 hours, the nano-aluminum hydroxide DAH3 that obtains.
100g nano-aluminum hydroxide DAH3 and macroporous aluminium oxide were mixed by weight 3: 1; The rare nitric acid of 2.4g (mass concentration 17%), 75g water are mixed, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained Comparative Examples alumina support DA3.
The character of table 1 embodiment of the invention and Comparative Examples gained alumina support
| Sample | A1 | A2 | A3 | DA1 | DA2 | DA3 |
| Pore volume/cm 3.g -1 | 0.96 | 1.12 | 0.88 | 1.6 | 2.3 | 1.30 |
| Specific area/m 2.g -1 | 195 | 234 | 188 | 224 | 265 | 226 |
| Can a few bore dia/nm | 32 | 35 | 41 | 18 | 45 | 23 |
| Pore size distribution, % | ||||||
| ＜6nm | 2.7 | 4.0 | 2.4 | 7.0 | 5.0 | 8.0 |
| 6-10nm | 4.3 | 14.4 | 3.4 | 16.0 | 9.0 | 20.0 |
| 10-20nm | 12.4 | 13.0 | 7 | 12.0 | 10.0 | 13.0 |
| 20-30nm | 13.5 | 15.6 | 5 | 13 | 8.0 | 7.0 |
| 30-60nm | 36.6 | 21.9 | 28.6 | 9.0 | 7.0 | 9.0 |
| 60-100nm | 26.3 | 23.1 | 15.6 | 7.0 | 6.0 | 11.0 |
| ＞100nm | 4.2 | 8.0 | 38 | 36.0 | 55.0 | 32.0 |
| Porosity/% | 45 | 57 | 52 | 76 | 82 | 78 |
| Intensity, N/mm | 18.0 | 25.0 | 23.0 | 6.4 | 2.7 | 7.0 |
| Bulk density/g.cm -3 | 0.54 | 0.58 | 0.55 | 0.47 | 0.31 | 0.42 |
Claims (12)
1. the preparation method of an alumina support comprises the steps:
(1) adopt the super solubilising micelle of fused salt legal system to be equipped with the nano-aluminum hydroxide gel,
(2) the nano-aluminum hydroxide gel of step (1) gained after drying,
(3) the nano-aluminum hydroxide xerogel of usefulness organic solvent extraction steps (2) gained,
(4) with the nano-aluminum hydroxide drying behind the solvent extraction, obtain nano-aluminum hydroxide;
(5) with the nano-aluminum hydroxide moulding of step (4) gained, drying and roasting obtain alumina support; The described organic solvent of step (3) is one or more in gasoline, diesel oil, benzinum, toluene, dimethylbenzene, normal heptane and the cyclohexane; The condition of described solvent extraction is as follows: described nano-aluminum hydroxide xerogel is 1: 1～5 with the volume of organic solvent ratio, 50～100 ℃ of temperature, normal pressure, 1～10 hour extracting time, extracting number of times 1～3 time.
2. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: 100～130 ℃ of baking temperatures, 1～30 hour drying time; The described drying condition of step (4) was as follows: 100～130 ℃ of dryings 1～30 hour.
3. in accordance with the method for claim 1, it is characterized in that in the described alumina support preparation process one or more in adding auxiliary agents of silicon, titanium, zirconium, magnesium, phosphorus, boron, lanthanum, iron, manganese, the calcium.
4. in accordance with the method for claim 3, it is characterized in that described auxiliary agent introduces with following one of at least method: I, before nano-aluminum hydroxide becomes glue, adopt the introducing of the super solubilising micelle of fused salt method; II, the mode with making beating after becoming glue add, and III, introduce with kneading method before moulding, IV, adopt infusion process to introduce after making alumina support.
5. in accordance with the method for claim 1, it is characterized in that the drying condition after the described moulding of step (5) is as follows: under 100～130 ℃ of temperature, carried out drying 1～30 hour; Described roasting condition is as follows: 180～1200 ℃ of roastings 4～80 hours, programming rate was 0.1～5.0 ℃/min.
6. in accordance with the method for claim 5, it is characterized in that the described roasting condition of step (5) is as follows: 180～300 ℃ of roasting temperatures 1～10 hour, 500～1200 ℃ of roastings 2～60 hours, programming rate was 1～5 ℃/min.
7. in accordance with the method for claim 1, it is characterized in that described forming method adopts the extruded moulding method.
8. in accordance with the method for claim 7, it is characterized in that in the described alumina support forming process, add peptizing agent, water and cosolvent; Described extrusion method process is as follows: described nano-aluminum hydroxide, peptizing agent, water and cosolvent mixed, and moulding in banded extruder then, controlled pressure is at 10～50MPa; Described peptizing agent is one or more in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and the sulfuric acid, and consumption is the 1wt%～15wt% of nano-aluminum hydroxide weight, and described water consumption is the 5wt%～100wt% of nano-aluminum hydroxide weight; In described cosolvent methyl alcohol, ethanol and the propyl alcohol one or more, consumption are the 1wt%～15wt% of nano-aluminum hydroxide weight.
9. in accordance with the method for claim 8, it is characterized in that in the aluminium oxide forming process, add in other the aluminium hydroxide, molecular sieve, adhesive one or more in the nano-aluminum hydroxide.
10. in accordance with the method for claim 9, it is characterized in that described other aluminium hydroxide is the nano-aluminum hydroxide that the nano-aluminum hydroxide gel that adopts the super solubilising micelle of fused salt method to obtain obtains after drying.
11. in accordance with the method for claim 9, it is characterized in that in the aluminium oxide forming process, earlier nano-aluminum hydroxide is mixed with adhesive, add then in the mixture of peptizing agent, water and cosolvent, again extruded moulding.
12. in accordance with the method for claim 10, it is characterized in that in the aluminium oxide forming process, earlier nano-aluminum hydroxide, other aluminium hydroxide are mixed with adhesive, add then in the mixture of peptizing agent, water and cosolvent, again extruded moulding.
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| CN105121347A (en) * | 2013-02-04 | 2015-12-02 | 俄罗斯工程技术中心 | Aluminum oxide |
| TW201442779A (en) * | 2013-02-07 | 2014-11-16 | Scient Design Co | Modified carrier for silver based ethylene oxide catalyst |
| CN108793210B (en) * | 2017-05-02 | 2020-04-10 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method thereof |
| CN108452806B (en) * | 2017-10-27 | 2021-01-01 | 中国石油天然气股份有限公司 | Coking naphtha dialkene saturation catalyst and preparation method thereof |
| CN111377467A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina and preparation method thereof |
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