CN105312091A - Alumina carrier and preparation method thereof - Google Patents
Alumina carrier and preparation method thereof Download PDFInfo
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- CN105312091A CN105312091A CN201410238328.7A CN201410238328A CN105312091A CN 105312091 A CN105312091 A CN 105312091A CN 201410238328 A CN201410238328 A CN 201410238328A CN 105312091 A CN105312091 A CN 105312091A
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Abstract
The invention relates to an alumina carrier, which has a specific surface area of 50-130 m<2>/g and a total pore volume of 0.5-1.0 ml/g, wherein the pore volume of the pore having a diameter of 2-10 nm in the carrier accounts for 4-15% of the total pore volume, the pore volume of the pore having a diameter of 10-20 nm in the carrier accounts for 40-60% of the total pore volume, the pore volume of the pore having a diameter of 20-50 nm in the carrier accounts for 1.0-5.0% of the total pore volume, and the pore volume of the large pore having a diameter of more than 50 nm and not more than 10 [mu]m in the carrier accounts for 20-50% of the total pore volume. According to the present invention, the catalyst obtained by loading the active component on the carrier has the good reaction performance when the catalyst is used for the olefin preparation reaction through low carbon alkane dehydrogenation.
Description
Technical field
The present invention is a kind of aluminium oxide and preparation method, specifically, is a kind of alumina support and preparation method.
Background technology
Propylene is a kind of important basic organic chemical industry raw material, is widely used in producing the multiple chemical products such as polypropylene, acetone, acrylonitrile, expoxy propane, acrylic acid.At present, propylene supply is mainly from the byproduct of naphtha pyrolysis ethene and petroleum catalytic cracking process.Since the nineties in last century, along with the continuous increase of propylene demand, traditional propylene production technology can not meet the demand of chemical industry to propylene, must accelerate development other alternative techniques technology.Wherein preparing propylene by dehydrogenating propane technique is of greatest concern.By 2010, the propylene production capacity from dehydrogenating propane device accounted for more than 5% of aggregated capacity, became the 3rd source of global propylene.The technology of industrialized Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane mainly contains the Oleflex technology of Uop Inc. and the Catofin technology of Lummus company at present.Oleflex technique adopts the moving-burden bed reactor of continuous catalyst regenerating, with Pt-Sn/Al
2o
3for catalyst, add K or Li etc. and carry out modification; Catofin technique adopts fixed bed reactors, with Cr
2o
3/ Al
2o
3for catalyst, catalysqt deactivation speed is fast, just need regenerate once every 15 minutes.
Propane catalytic dehydrogenating reaction limits by thermodynamical equilibrium, and high temperature and low pressure are conducive to the carrying out reacted.But too high reaction temperature can make Deposition During Propane Pyrolysis react to be increased, and carbon distribution is serious, and catalyst deactivation rate is accelerated, therefore develop the key that the propane dehydrogenation catalyst with high activity, high selectivity and high stability becomes this technology.
Load type platinum is catalyst based is an important class in catalyst for dehydrogenation of low-carbon paraffin, being carrier usually, carrying out modification, to improve the activity and selectivity of catalyst by adding other components with aluminium oxide.USP4506032 discloses a kind of dehydrogenation component, and take aluminium oxide as carrier, load has Pt Group Component, IVA component, alkali metal or alkaline earth metal component and halogen component.The preferred γ of alumina support-Al
2o
3or η-Al
2o
3.Wherein the atomic ratio of alkali metal or alkaline-earth metal and Pt race metal is greater than 10.This catalyst is used for the dehydrogenating low-carbon alkane containing 2 ~ 5 carbon atoms by this patent.
USP4914075 discloses a kind of dehydrogenation component, at θ-Al
2o
3upper load has VIII race's noble metal component, alkali metal or alkaline earth metal component and is selected from the component of tin, germanium, lead, indium, gallium, thallium or its mixture.The specific area of alumina support is 50 ~ 120m
2/ g, apparent bulk density is greater than 0.5g/cm
3, the preferred caesium of alkali metal in catalyst, Pt/Sn mol ratio is 0.851 ~ 0.912.
CN1069226C discloses a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, and this method take aluminium oxide as carrier, step impregnation IVA race metal, Pt race metal, alkali metal, halogen and element sulphur.Need to use steam treatment after flooding IVA element and Pt race element.Described alkali metal is selected from lithium or potassium.
CN102049267A discloses a kind of catalyst of preparing propylene by dehydrogenating propane, take aluminium oxide as carrier, and load has Pt race metal, IVA metal, potassium, cerium or samarium and halogen.Wherein the mol ratio of IVA metal and Pt race metal is 1.0 ~ 1.8, and the mol ratio of cerium or samarium and Pt race metal is 2.2 ~ 4.9.
CN1265878C discloses a kind of dehydrogenation catalyst composition, the second component of this carbon monoxide-olefin polymeric mainly containing the VIIIth race's noble metal component, IA or IIA race metal and be selected from the three components of tin, germanium, lead, indium, gallium, thallium and composition thereof, load on the alumina support.Described aluminium oxide is mainly containing θ-Al
2o
3, there is 50 ~ 120m
2the surface area of/g and at least 0.5g/cm
3apparent bulk density, wherein the mol ratio of the VIIIth race's noble metal component and three components is 1.5 ~ 1.7.The preferred potassium of alkali metal, its content is based on composition total weight 0.9 ~ 1.1%.
Summary of the invention
The object of this invention is to provide a kind of alumina support and preparation method, this carrier has suitable macropore distribution proportion, and the catalyst obtained after load active component reacts for manufacturing olefin by low-carbon alkane dehydrogenation, has good reactivity worth.
Alumina support provided by the invention, has 50 ~ 130m
2the specific area of/g, the total pore volume of 0.5 ~ 1.0mL/g, in carrier diameter be the pore volume in the hole of 2 ~ 10 nanometers account for total pore volume 4 ~ 15%, diameter be the pore volume in the hole of 10 ~ 20 nanometers account for total pore volume 40 ~ 60%, diameter be the pore volume in the hole of 20 ~ 50 nanometers account for total pore volume 1.0 ~ 5.0%, diameter is greater than 50 nanometers but the pore volume being not more than the macropore of 10 microns accounts for 20 ~ 50% of total pore volume.
The present invention adds expanding agent in carrier preparation process, and the macropore ratio of 50nm ~ 10 in the alumina support obtained μm is increased, and catalyst obtained after load active component has higher appearance carbon ability, and stability is improved.
Detailed description of the invention
The present invention is in carrier preparation process, add expanding agent, then through two-stage roasting, make diameter in carrier be that the macropore pro rate of the mesopore of 2 ~ 50nm and 50nm ~ 10 μm is reasonable, the ratio of macropore obviously increases, and in middle pore size distribution, larger proportion is occupied in the hole of 10 ~ 20nm.The catalyst of manufacturing olefin by low-carbon alkane dehydrogenation is obtained with this carrier, mesopore is wherein conducive to the dehydrogenation reaction of low-carbon alkanes, macropore is conducive to the diffusion in the catalyst of low-carbon alkanes gas, increase the transfer rate of material, reduce the carbon deposit precursor time of staying on a catalyst, and make catalyst have the ability of higher accommodation carbon distribution, anti-carbon deposition ability improves.When this catalyst is used for propane catalytic dehydrogenating reaction, there is higher conversion of propane and Propylene Selectivity, the good stability of catalyst, and there is good regenerability.
The specific area preferably 80 ~ 120m of carrier of the present invention
2/ g, specific area is greater than 130m
2during/g, the acidic site of carrier increases, and cracking side-reaction can be caused to increase, and pyroreaction can cause the minimizing of alumina ratio surface area and the change of structural behaviour for a long time; Specific area is less than 50m
2during/g, enough active surfaces cannot be provided to disperse for active metal, and the activated centre quantity of catalyst is lower, and catalytic activity is restricted.
The pore volume of alumina support provided by the invention preferably 0.6 ~ 0.75 ml/g.Most probable pore size is 10 ~ 20nm.
Alumina support provided by the invention preferably has following pore size distribution: diameter be the pore volume in the hole of 2 ~ 10 nanometers account for total pore volume 7 ~ 15%, diameter be the pore volume in the hole of 10 ~ 20 nanometers account for total pore volume 43 ~ 60%, diameter be the pore volume in the hole of 20 ~ 50 nanometers account for total pore volume 1.0 ~ 5.0%, diameter is greater than 50 nanometers but the pore volume being not more than the macropore of 10 microns accounts for 22 ~ 48% of total pore volume.
Aluminium oxide of the present invention is preferably θ-aluminium oxide.Carrying alumina shape can be spherical, graininess, sheet shape, bar shaped or cloverleaf pattern, preferably spherical.For using moving-burden bed reactor in course of reaction, continuous catalyst regenerating need be carried out, need ball type carrier be used, be beneficial to the conveying of catalyst in reaction and regenerative process.Above-mentioned spherical alumina support drips ball forming by oil ammonia column or deep fat post, and bar shaped or cloverleaf pattern carrier can adopt conventional extrusion moulding preparation.
For the catalyst used in moving-burden bed reactor, catalyst needs repeated regeneration to use.Catalyst used carrier shape is preferably spherical.Ball type carrier particle diameter is 1.0 ~ 5.0mm, preferably 1.4 ~ 2.0mm.When particle diameter is less than 1.0mm, catalyst buildup can be caused tight, cause bed pressure drop to increase, be unfavorable for design and the operation of technical process.In addition, easily cause the adherent problem of so-called catalyst compared with the spheric catalyst of small particle diameter, namely by the impact that reaction logistics promotes, bead rests near reactor wall and cannot flow, the serious carbon deposit of easy generation catalyst, and cause catalyst flowing or carry the problems such as not smooth.When particle diameter is greater than 5.0mm, can cause the lifting difficulty of catalyst, simultaneously because the distance between catalyst shell and the centre of sphere is comparatively large, reactant increases to the diffusion length of the centre of sphere, is unfavorable for the catalytic action playing active catalytic center in ball.In catalyst regeneration process, also there is diffusion problem in burning process, and the coke of the bead inside that particle diameter is larger possibly cannot be eliminated easily.
In moving bed process, catalyst needs continuous-flow between reaction and regeneration zones, catalyst can occur to rub and collide with reactor and conveyance conduit, and this just requires that catalyst has larger intensity and abrasion resistance, and the crushing strength of carrier of the present invention is greater than 30N.In order to catalyst proper flow and conveying, catalyst also should have suitable bulk density, and the bulk density of carrier of the present invention is preferably 0.5 ~ 1.0g/cm
3.
The preparation method of ball type carrier of the present invention, comprises the steps:
(1) in aluminium hydroxide, add sour peptization, obtained alumina sol, adds expanding agent in alumina sol, drips ball forming,
(2) after (1) step being dripped the wet bulb drying after ball forming, carry out one section of roasting in 620 ~ 680 DEG C, then be warming up to 900 ~ 1100 DEG C and carry out two-stage calcination and obtain carrier.
In said method, (1) step for drip ball forming with alumina sol, the preferred C of the expanding agent added in Alumina gel
10~ C
16hydrocarbon, urea or ammonium carbonate salts.Described C
10~ C
16the preferred kerosene of hydrocarbon, the preferred carbonic hydroammonium of ammonium carbonate salts or ammonium carbonate.
The mass ratio of the aluminium oxide contained in the expanding agent added and Alumina gel is 0.05 ~ 0.6, preferably 0.1 ~ 0.5.
The method preparing alumina sol can have multiple, as alchlor and ammoniacal liquor are reacted at the temperature of 60 ~ 80 DEG C, then filter, wash, in filter cake (aluminium hydroxide), add acid solution obtain, also can make slurries directly to adding in aluminium hydrate powder water, then add sour peptization in slurries.The preferred nitric acid of acid that peptization is used or hydrochloric acid, also can use organic acid, as acetic acid or citric acid.Carry out peptization with organic acid preferably to use with nitric acid or mixed in hydrochloric acid.
When expanding agent used is C
10~ C
16hydrocarbon time, in Alumina gel, preferably add surfactant as demulsifier.Described surfactant can be AEO, NPE.
In said method, in the alumina sol preferably obtained in (1) step, add the compound of the modified metal component being selected from tin, germanium, lead, indium, gallium or thallium.The chloride of the preferred described metal component of compound of described modified metal component, nitrate or organic compound, more preferably stannous bromide, stannous chloride, butter of tin, butter of tin pentahydrate or tetrabutyltin.
(1) method of in step, alumina sol (Alumina gel) being carried out dripping ball forming can be that hot forming oil column or oil ammonia column are shaping.When dripping ball forming, the concentration of alumina sol should control to be 15 ~ 23 quality % (in alumina contents), Alumina gel excessive concentration, viscosity is also high, the slurries flowed out from pin hole when dripping ball not easily fragment into and drip, and should deform and become aspherical, even occur bracing wire phenomenon; Alumina gel concentration is too low, and viscosity is also low, slurry droplet easily broken and not balling-up when falling into oil.
The inventive method (2) step is the wet bulb after shaping is carried out roasting obtain ball type carrier, and roasting is divided into two sections, and one section of roasting forms macropore, and two-stage calcination forms θ-aluminium oxide.All preferably 1 ~ 20 hour two-stage roasting time.Gained carrier is alumina support or the alumina support containing modified metal, alumina support wherein containing modified metal component also can be prepared by the method for dipping, compound by the modified metal component of above-mentioned stanniferous, germanium, lead, indium, gallium or thallium is mixed with maceration extract, with the alumina support that impregnation fluid (2) step is obtained, namely solid drying after dipping, roasting is obtained the alumina support containing modified metal component.
When (1) step expanding agent used is C
10~ C
16hydrocarbon time, drip after ball forming, after (2) step carries out one section of roasting, with the air-treatment 1 ~ 15 hour of moisture vapor, the water content in air of process is preferably 4 ~ 30 quality %, more preferably 4 ~ 20 quality %, and treatment temperature is preferably identical with one section of sintering temperature.
After alumina support load active component provided by the invention, can be made into catalyst for dehydrogenation of low-carbon paraffin, the method of Kaolinite Preparation of Catalyst preferably includes: by the above-mentioned solution impregnation of alumina support containing VIII race's metal and halogen-containing compound containing modified metal component, dry, 400 ~ 650 DEG C of roastings, again by the water soluble compound solution impregnation containing IA race metal, dry, 400 ~ 650 DEG C of roastings.
In above-mentioned method for preparing catalyst, when introducing VIII race's metal and halogen in carrier, the preferred chloroplatinic acid of compound containing VIII race's metal that preparation maceration extract is used or ammonium chloroplatinate.For making VIII race's metal be evenly distributed in the carrier, in the maceration extract of preparation, add halogen-containing compound, to form competitive Adsorption.The preferred trichloroacetic acid of halogen-containing compound added in maceration extract or hydrogen chloride, more preferably hydrogen chloride.
When introducing IA race metal in carrier, the preferred potassium hydroxide of water soluble compound containing IA race metal, potassium nitrate or potassium chloride that preparation maceration extract is used.
In said method, when introducing active component by dipping, dipping temperature preferably 20 ~ 70 DEG C.Gu the liquid/than being 1.0 ~ 2.0ml/g of maceration extract and carrier during dipping, after introducing active component after each dipping, gained solid all needs drying, roasting, baking temperature preferably 100 ~ 300 DEG C, sintering temperature preferably 500 ~ 630 DEG C.
In catalyst prepared by said method, the VIII race's tenor being benchmark with butt aluminium oxide is 0.1 ~ 1.0 quality %, the second metal component content preferably 0.1 ~ 1.0 quality %, IA race tenor preferably 0.5 ~ 2.0 quality %, content of halogen preferably 0.3 ~ 3.0 quality % preferably.
The preferred platinum of VIII race's metal in described catalyst, the preferred potassium of IA race metal, the preferred tin of the second metal component, the preferred chlorine of halogen.
Catalyst prepared by said method needs reduction before use, and the preferred hydrogen of the gas for reducing, also can adopt CO or other reducibility gas.Reduction temperature preferably 500 ~ 650 DEG C, preferably 0.5 ~ 10 hour recovery time.Reduction can be carried out before catalyst loads reactor, also can carry out before dehydrogenation reaction after catalyst loads reactor.
Described catalyst is applicable to the reaction of manufacturing olefin by low-carbon alkane dehydrogenation.By low-carbon alkanes in presence of hydrogen with catalyst for dehydrogenation of low-carbon paraffin at 400 ~ 800 DEG C, preferably 550 ~ 650 DEG C, react under the condition of pressure 0.1 ~ 1.0MPa, preferably 0.1 ~ 0.5MPa (absolute pressure).
In course of reaction, the suitable mass space velocity of low-carbon alkanes and catalyst exposure is 0.1 ~ 20h
-1, more preferably 0.5 ~ 10h
-1.
Above-mentioned dehydrogenation reaction also can be selected steam, argon, methane, ethane, carbon dioxide, nitrogen etc. to mix with low-carbon alkanes as diluted material and pass into reactor, and preferred diluted material is hydrogen.When selecting hydrogen, mol ratio preferably 0.1 ~ 10:1, the more preferably 0.3 ~ 3:1 of hydrogen and low-carbon alkanes.
Above-mentioned low-carbon alkanes is propane, butane or pentane, and described butane is normal butane, iso-butane.Reacting preferred low-carbon alkanes is propane or iso-butane.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
Get 27g aluminium flake, add the hydrochloric acid solution that 610 grams of concentration are 18 quality %, aluminium flake is dissolved, obtain the solution that alchlor content is 4 quality %, proceeded to neutralizing tank, the concentration adding 850 grams is the ammoniacal liquor of 6 quality %, 60 DEG C mix, and pH value is 7.5 ~ 8.5.Generate aluminium hydroxide after filtration, washing, the nitric acid acidifying that 9mL volume ratio is 1:1 is added in filter cake, the solution of 40mL containing 30 grams of ureas and the hydrochloric acid solution containing 32 grams of stannous chlorides is added under stirring, measuring containing Sn in solution is made to be 0.32% of butt quality of alumina, stir acidifying in 1 hour, then 30 grams of kerosene are added and 3 grams of NPEs stir 1 hour, with Al in colloidal sol
2o
3the solid content of meter is 20 quality %.This colloidal sol is instilled in the oil ammonia column that upper strata is oil phase, lower floor is ammoniacal liquor phase and drips ball forming.Described oil phase is kerosene, ammoniacal liquor mutually in the concentration of ammoniacal liquor be 8 quality %.Wet bulb ammoniacal liquor mutually in solidification 1 hour, taking-up deionized water rinsing, 60 DEG C of dryings 6 hours, 120 DEG C of dryings 10 hours, 650 DEG C are carried out one section of roasting 4 hours in air stream, then be process 10 hours in the air of 5 volume % at 650 DEG C at vapour content, be warming up to 1000 DEG C and carry out two-stage calcination 4 hours, obtained stanniferous θ-Al
2o
3carrier a, its physical property is in table 1.
Example 2
Alumina support is prepared by the method for example 1, unlike getting 132 grams of aluminium hydrate powders, (German Sasol company produces, trade mark SB, alumina content is quality 76%), add 100mL deionized water, stir and make its pulp in 1 hour, then to add 9mL volume ratio be that the nitric acid acidifying of 1:1 obtains Alumina gel, obtained stanniferous θ-Al
2o
3the physical property of carrier b is in table 1.
Example 3
Prepare alumina support by the method for example 1, unlike under agitation, in the colloidal sol after acidifying, add the aqueous solution containing 40g carbonic hydroammonium, and do not add kerosene and NPE, obtained stanniferous θ-Al
2o
3the physical property of carrier c is in table 1.
Example 4
Alumina support is prepared by the method for example 1, unlike adding 40 grams of kerosene and 4 grams of AEOs in the Alumina gel after acidifying, obtained stanniferous θ-Al
2o
3the physical property of carrier d is in table 1.
Example 5
Alumina support is prepared by the method for example 1, unlike adding 15 grams of kerosene and 2 grams of AEOs in the colloidal sol after acidifying, obtained stanniferous θ-Al
2o
3the physical property of carrier e is in table 1.
Example 6
Alumina support is prepared by the method for example 1, unlike not adding urea and the hydrochloric acid solution containing 32 grams of stannous chlorides in the Alumina gel after acidifying, obtained θ-Al
2o
3carrier h, physical property is in table 1.
Get above-mentioned not stanniferous θ-Al
2o
3carrier h, floods 4 hours in 25 DEG C with the hydrochloric acid solution of the sub-tin of chloride containing, the tin (relative to butt aluminium oxide) containing 0.32 quality % in maceration extract, Gu liquid/than being 1.8mL/g.After dipping, gained solid was in 120 DEG C of dryings 12 hours, 500 DEG C of roasting 4h, obtained stanniferous θ-Al
2o
3carrier h'.
Example 7
Prepare alumina support by the method for example 1, unlike the air-treatment carrier without moisture vapor after one section of roasting, but directly carry out two-stage calcination, obtained stanniferous θ-Al
2o
3the physical property of carrier j is in table 1.
Comparative example 1
Prepare alumina support by the method for example 1, unlike by after alumina globule drying 650 DEG C of roastings 4 hours, obtained stanniferous γ-Al
2o
3the physical property of carrier f is in table 1.
Comparative example 2
Preparing alumina support by the method for example 1, unlike not adding kerosene and NPE in the Alumina gel of acidifying, and after aluminium oxide is carried out one section of roasting, directly carrying out two-stage calcination, obtained stanniferous θ-Al
2o
3the physical property of carrier g is in table 1.
Example 8
Prepare catalyst for dehydrogenation of low-carbon paraffin.
Get the stanniferous alumina globule carrier that above-mentioned each example and comparative example are obtained respectively, flood 4 hours in 25 DEG C with the maceration extract containing chloroplatinic acid and hydrochloric acid, containing the platinum of 0.30%, the chlorine (all relative to butt quality of alumina) of 2.0% in maceration extract, Gu liquid/than being 1.8mL/g.After dipping by solid in 120 DEG C of dryings 12 hours, 500 DEG C of roasting 4h.Solid after roasting is flooded 4 hours in 25 DEG C with the potassium nitrate solution containing potassium 1.0 quality % (relative to butt quality of alumina) again, Gu liquid/than being 1.4mL/g.After dipping, solid was in 120 DEG C of dryings 12 hours, 600 DEG C of roasting 4h.By the oxidized catalyst of gained after roasting in 550 DEG C with hydrogen reducing 2 hours, obtain dehydrogenation.The platinum content being benchmark with butt aluminium oxide in catalyst is 0.30 quality %, Theil indices is 0.32 quality %, potassium content is 1.0 quality %, chlorinity is 1.0 quality %.
Obtained catalyst represents with the capitalization of corresponding bearer number.
Table 1
In table 1, pore diameter range left side numeral is not included in scope, and digits right is included in scope, as 2 ~ 10nm represents the hole of 2nm< diameter≤10nm.
Example 9 ~ 17
Following instance evaluates the reactivity worth of dehydrogenation.
In micro-reactor, load 6 milliliters of catalyst, with the mist of hydrogen and propane for raw material, the purity of propane is greater than 99.9%, 620 DEG C, 0.21MPa (absolute pressure), propane feed mass space velocity be 3.5h
-1, hydrogen/propane mol ratio be react under the condition of 0.5:1, every 1 hour, sampling should be carried out carries out chromatography.Each catalyst at the conversion of propane of differential responses time and Propylene Selectivity in table 2.
Table 2
As shown in Table 2, the catalyst prepared by carrier of the present invention, than the catalyst prepared by comparative example carrier, has higher conversion of propane, and react 50 hours, the selective of propylene is greater than 95%, and the stability of catalyst is also better.The total carbon deposition of reaction 50 hours catalyst is low, has good reactivity worth.
Claims (12)
1. an alumina support, has 50 ~ 130m
2the specific area of/g, the total pore volume of 0.5 ~ 1.0mL/g, in carrier diameter be the pore volume in the hole of 2 ~ 10 nanometers account for total pore volume 4 ~ 15%, diameter be the pore volume in the hole of 10 ~ 20 nanometers account for total pore volume 40 ~ 60%, diameter be the pore volume in the hole of 20 ~ 50 nanometers account for total pore volume 1.0 ~ 5.0%, diameter is greater than 50 nanometers but the pore volume being not more than the macropore of 10 microns accounts for 20 ~ 50% of total pore volume.
2. according to carrier according to claim 1, it is characterized in that diameter in described alumina support be the pore volume in the hole of 2 ~ 10 nanometers account for total pore volume 7 ~ 15%, diameter be the pore volume in the hole of 10 ~ 20 nanometers account for total pore volume 43 ~ 60%, diameter be the pore volume in the hole of 20 ~ 50 nanometers account for total pore volume 1.0 ~ 5.0%, diameter is greater than 50 nanometers but the pore volume being not more than the macropore of 10 microns accounts for 22 ~ 48% of total pore volume.
3., according to the carrier described in claim 1 or 2, it is characterized in that described aluminium oxide is θ-aluminium oxide.
4., according to the carrier described in claim 1 or 2, it is characterized in that containing the modified metal component being selected from tin, germanium, lead, indium, gallium or thallium in described carrier, described modified metal constituent content with butt alumina support for benchmark is 0.1 ~ 2.0 quality %.
5. a preparation method for alumina support described in claim 1, comprises the steps:
(1) in aluminium hydroxide, add sour peptization, obtained alumina sol, adds expanding agent in alumina sol, drips ball forming,
(2) after (1) step being dripped the wet bulb drying after ball forming, carry out one section of roasting in 620 ~ 680 DEG C, then be warming up to 900 ~ 1100 DEG C and carry out two-stage calcination and obtain carrier.
6. in accordance with the method for claim 5, it is characterized in that the expanding agent described in (1) step is C
10~ C
16hydrocarbon, urea or ammonium carbonate salts.
7. in accordance with the method for claim 6, it is characterized in that described C
10~ C
16hydrocarbon be kerosene, ammonium carbonate salts is carbonic hydroammonium or ammonium carbonate.
8. the mass ratio that in accordance with the method for claim 5, it is characterized in that the aluminium oxide contained in the expanding agent that adds in (1) step and Alumina gel is 0.05 ~ 0.6.
9. in accordance with the method for claim 5, it is characterized in that when expanding agent used is C
10~ C
16hydrocarbon time, drip after ball forming, after (2) step carries out one section of roasting, with the air-treatment 1 ~ 15 hour of moisture vapor, the water content in air of process is 4 ~ 30 quality %.
10. in accordance with the method for claim 5, it is characterized in that the compound adding the modified metal component being selected from tin, germanium, lead, indium, gallium or thallium in the alumina sol that obtains in (1) step.
11. in accordance with the method for claim 10, it is characterized in that the compound of described modified metal component is the chloride of described metal component, nitrate or organic compound.
12. in accordance with the method for claim 10, it is characterized in that the compound of described modified metal component is stannous bromide, stannous chloride, butter of tin, butter of tin pentahydrate or tetrabutyltin.
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| CN108187760A (en) * | 2016-12-08 | 2018-06-22 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof and dehydrogenation and its application |
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| CN111432926A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Catalyst and process for the selective conversion of hydrocarbons |
| CN113171801A (en) * | 2020-11-30 | 2021-07-27 | 谷育英 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof |
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| CN106582630A (en) * | 2016-12-05 | 2017-04-26 | 西安凯立新材料股份有限公司 | Platinum macroporous aluminum oxide catalyst for preparing propylene through propane dehydrogenation |
| CN106582630B (en) * | 2016-12-05 | 2019-08-30 | 西安凯立新材料股份有限公司 | A kind of platinum catalyst macropore alumina agent of preparing propylene by dehydrogenating propane |
| CN108187760A (en) * | 2016-12-08 | 2018-06-22 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof and dehydrogenation and its application |
| CN108686713A (en) * | 2017-04-12 | 2018-10-23 | 中国石油化工股份有限公司 | Alumina support and preparation method thereof and dehydrogenation and its application |
| CN111432926A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Catalyst and process for the selective conversion of hydrocarbons |
| CN109529811A (en) * | 2018-12-29 | 2019-03-29 | 杨斌 | Alumina support, salic carried catalyst preparation method and catalyst application |
| CN109529827A (en) * | 2018-12-29 | 2019-03-29 | 杨斌 | A kind of alumina support, preparation method containing carried catalyst and catalyst application |
| CN109569740A (en) * | 2018-12-29 | 2019-04-05 | 杨斌 | A kind of alumina support and preparation method and application |
| CN113171801A (en) * | 2020-11-30 | 2021-07-27 | 谷育英 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof |
| CN115364837A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
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