CN105312091B - A kind of alumina support and preparation method - Google Patents
A kind of alumina support and preparation method Download PDFInfo
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Abstract
A kind of alumina support, there is 50~130m2/ g specific surface area, 0.5~1.0ml/g total pore volume, the pore volume in a diameter of 2~10 nanometers of hole accounts for the 4~15% of total pore volume in carrier, the pore volume in a diameter of 10~20 nanometers of hole accounts for the 40~60% of total pore volume, the pore volume in a diameter of 20~50 nanometers of hole accounts for the pore volume of macropore of the 1.0~5.0% of the total pore volume, diameter more than 50 nanometers but no more than 10 microns and accounts for the 20~50% of total pore volume.The catalyst obtained after the carrier loaded active component reacts for manufacturing olefin by low-carbon alkane dehydrogenation, has preferable reactivity worth.
Description
Technical field
The present invention is a kind of aluminum oxide and preparation method, is a kind of alumina support and preparation method specifically.
Background technology
Propylene is a kind of important basic organic chemical industry raw material, is widely used in producing polypropylene, acetone, acrylonitrile, ring
A variety of chemical products such as Ethylene Oxide, acrylic acid.At present, propylene supply is split essentially from naphtha pyrolysis ethene and oil catalysis
The byproduct of change process.Since the nineties in last century, with being continuously increased for propylene demand, traditional propylene production technology
Can not meet the needs of chemical industry is to propylene, it is necessary to accelerate development other alternative techniques technologies.Wherein dehydrogenating propane system
Propylene technique is of greatest concern.By 2010, the propylene production capacity from dehydrogenating propane device accounted for more than the 5% of aggregated capacity, turns into complete
3rd source of ball propylene.The technology of current industrialized Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane mainly has Uop Inc.
Oleflex technologies and the Catofin technologies of Lummus companies.Oleflex techniques are anti-using the moving bed of continuous catalyst regenerating
Device is answered, with Pt-Sn/Al2O3For catalyst, addition K or Li etc. is modified；Catofin techniques use fixed bed reactors, with
Cr2O3/Al2O3For catalyst, catalyst inactivation speed is fast, need to just be regenerated once every 15 minutes.
Propane catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, and high temperature and low pressure are advantageous to the progress of reaction.It is but too high
Reaction temperature can make Deposition During Propane Pyrolysis reaction increase, carbon distribution is serious, catalyst deactivation rate accelerate, therefore develop with high activity,
The propane dehydrogenation catalyst of high selectivity and high stability turns into the key of the technology.
Support type platinum based catalyst is important one kind in catalyst for dehydrogenation of low-carbon paraffin, generally using aluminum oxide as carrier,
It is modified by adding other components, to improve the activity and selectivity of catalyst.USP4506032 discloses a kind of dehydrogenation
Catalytic component, using aluminum oxide as carrier, it is loaded with Pt Group Components, IV component A, alkali metal or alkaline earth metal component and halogen
Plain component.Preferred γ-the Al of alumina support2O3Or η-Al2O3.The wherein atomic ratio of alkali metal or alkaline-earth metal and Pt races metal
More than 10.This catalyst is used for the dehydrogenating low-carbon alkane containing 2~5 carbon atoms by the patent.
USP4914075 discloses a kind of dehydrogenation component, in θ-Al2O3On be loaded with VIII race's noble metal component, alkali
Metal or alkaline earth metal component and the component selected from tin, germanium, lead, indium, gallium, thallium or its mixture.The ratio surface of alumina support
Product is 50~120m2/ g, apparent bulk density are more than 0.5g/cm3, the preferred caesium of alkali metal in catalyst, Pt/Sn mol ratios are 0.851
~0.912.
CN1069226C discloses a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, the method using aluminum oxide as carrier,
Step impregnation group IVA metal, Pt races metal, alkali metal, halogen and element sulphur.Impregnate IV element A and Pt races element
After need to use steam treatment.Described alkali metal is selected from lithium or potassium.
CN102049267A discloses a kind of catalyst of preparing propylene by dehydrogenating propane, using aluminum oxide as carrier, is loaded with Pt
Race's metal, IVA metals, potassium, cerium or samarium and halogen.The mol ratio of wherein IVA metals and Pt races metal is 1.0~1.8, cerium or samarium
Mol ratio with Pt races metals is 2.2~4.9.
CN1265878C discloses a kind of dehydrogenation catalyst composition, and the carbon monoxide-olefin polymeric mainly contains the VIIIth expensive gold of race
Belong to the second component of component, I A or Group IIA metal and the third component selected from tin, germanium, lead, indium, gallium, thallium and its mixture,
Load is on the alumina support.Main-the Al containing θ of the aluminum oxide2O3, there is 50~120m2/ g surface area and at least 0.5g/
cm3Apparent bulk density, wherein the mol ratio of the VIIIth race's noble metal component and third component be 1.5~1.7.Alkali metal is preferred
Potassium, its content are 0.9~1.1% based on composition total weight.
The content of the invention
It is an object of the invention to provide a kind of alumina support and preparation method, the carrier has suitable big pore size distribution ratio
, the catalyst obtained after load active component reacts for manufacturing olefin by low-carbon alkane dehydrogenation, has preferable reactivity worth.
Alumina support provided by the invention, there is 50~130m2/ g specific surface area, 0.5~1.0mL/g total hole body
Long-pending, the pore volume in a diameter of 2~10 nanometers of hole accounts for the 4~15% of total pore volume, a diameter of 10~20 nanometers of hole in carrier
Pore volume account for the 40~60% of total pore volume, the pore volume in a diameter of 20~50 nanometers of hole account for total pore volume 1.0~
5.0%th, diameter is more than 50 nanometers but the pore volume of the macropore no more than 10 microns accounts for the 20~50% of total pore volume.
The present invention adds expanding agent in carrier preparation process, makes the macropore of 50nm~10 μm in obtained alumina support
Ratio increase, obtained catalyst has higher appearance carbon ability after load active component, and stability is improved.
Embodiment
The present invention adds expanding agent in carrier preparation process, then by two-stage roasting, make a diameter of 2 in carrier~
50nm mesopore and the macropore pro rate of 50nm~10 μm are reasonable, and the ratio of macropore substantially increases, 10 in middle pore size distribution~
Larger proportion is occupied in 20nm hole.The catalyst of manufacturing olefin by low-carbon alkane dehydrogenation is made with the carrier, mesopore therein is advantageous to
The dehydrogenation reaction of low-carbon alkanes, macropore are advantageous to the diffusion of low-carbon alkanes gas in the catalyst, increase the transfer rate of material,
The residence time of carbon deposit precursor on a catalyst is reduced, and the ability for making catalyst that there is higher receiving carbon distribution, anti-product
Charcoal ability improves.When the catalyst is used for propane catalytic dehydrogenating reaction, there is higher conversion of propane and Propylene Selectivity, urge
The stability of agent is good, and has good regenerability.
The specific surface area of carrier of the present invention preferably 80~120m2/ g, specific surface area are more than 130m2During/g, the acid of carrier
Property site increase, cracking side-reaction can be caused to increase, and prolonged pyroreaction can cause subtracting for alumina ratio surface area
Few and structural behaviour change；Specific surface area is less than 50m2During/g, enough active surfaces can not be provided and disperseed for active metal,
The activated centre quantity of catalyst is relatively low, and catalytic activity is restricted.
Preferably 0.6~0.75 ml/g of the pore volume of alumina support provided by the invention.Most probable pore size be 10~
20nm。
Alumina support provided by the invention preferably has following pore size distribution：The hole body in a diameter of 2~10 nanometers of hole
Product account for the 7~15% of the total pore volume, pore volume in a diameter of 10~20 nanometers of hole account for total pore volume 43~60%, it is a diameter of
It is big more than 50 nanometers but no more than 10 microns that the pore volume in 20~50 nanometers of hole accounts for the 1.0~5.0% of total pore volume, diameter
The pore volume in hole accounts for the 22~48% of total pore volume.
Aluminum oxide of the present invention is preferably θ-aluminum oxide.Carrying alumina shape can be spherical, graininess, piece shape,
It is bar shaped or cloverleaf pattern, preferably spherical.For using moving-burden bed reactor during the course of the reaction, catalyst need to be carried out continuously again
Raw, ball type carrier need to be used, so that catalyst is reacting and the conveying in regenerative process.Above-mentioned spherical alumina support can
By oil ammonia column or deep fat post drips ball forming, bar shaped or cloverleaf pattern carrier can use conventional extrusion moulding to prepare.
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, it can cause to urge
Agent accumulation is close, causes bed pressure drop to increase, is unfavorable for the design and operation of technical process.It is in addition, spherical compared with small particle
Catalyst easily causes the adherent problem of so-called catalyst, i.e., being promoted by reaction stream is influenceed, and it is attached that bead rests on reactor wall
It can not closely flow, the serious carbon deposit of catalyst easily occurs, and trigger catalyst to flow or convey the problems such as not smooth.Particle diameter is more than
During 5.0mm, the lifting of catalyst can be caused difficult, simultaneously as in larger distance between catalyst shell and the centre of sphere, reactant to
The diffusion length increase of the centre of sphere, is unfavorable for playing the catalytic action at active catalytic center in ball.In catalyst regeneration process, burn
There is also diffusion problem, the coke inside the larger bead of particle diameter possibly can not eliminate burnt process easily.
In moving bed process, catalyst needs continuous flowing between reaction and regeneration zones, and catalyst can be with reaction
Friction and collision occur for device and conveyance conduit, and this requires catalyst to have larger intensity and abrasion resistance, carrier of the present invention
Crushing strength be more than 30N.For catalyst proper flow and conveying, catalyst should also have suitable heap density, the present invention
The heap density of carrier is preferably 0.5~1.0g/cm3。
The preparation method of ball type carrier of the present invention, comprises the following steps：
(1) sour peptization is added in aluminium hydroxide, alumina sol is made, expanding agent is added in alumina sol, is dripped
Ball forming,
(2) after the wet bulb after (1) step drips ball forming is dried, one section of roasting is carried out in 620~680 DEG C, then be warming up to 900
~1100 DEG C carry out two-stage calcination and carrier are made.
In the above method, (1) step is the preferred C of expanding agent added in Alumina gel with alumina sol drips ball forming10~
C16Hydrocarbon, urea or ammonium carbonate salts.Described C10~C16The preferred kerosene of hydrocarbon, the preferred ammonium hydrogen carbonate of ammonium carbonate salts or ammonium carbonate.
The mass ratio of the aluminum oxide contained in the expanding agent and Alumina gel of addition is 0.05~0.6, preferably 0.1~0.5.
Prepare the method for alumina sol can have it is a variety of, such as by alchlor and ammoniacal liquor at a temperature of 60~80 DEG C it is anti-
Should, then filter, wash, acid solution is added into filter cake (aluminium hydroxide) and is made, directly can also be added into aluminium hydrate powder
Slurries are made in water, then sour peptization is added into slurries.Acid preferably nitric acid or hydrochloric acid used in peptization, it is also possible to organic acid, such as second
Acid or citric acid.Peptization is carried out with organic acid preferably to use with nitric acid or mixed in hydrochloric acid.
When expanding agent used is C10~C16Hydrocarbon when, preferably in Alumina gel add surfactant as demulsifier.Institute
The surfactant stated can be AEO, NPE.
In the above method, added preferably in alumina sol made from (1) step selected from tin, germanium, lead, indium, gallium or thallium
The compound of modified metal component.Chloride, the nitrate of the preferably described metal component of compound of the modified metal component
Or organic compound, more preferably stannous bromide, stannous chloride, butter of tin, butter of tin pentahydrate or tetrabutyltin.
(1) can be hot forming oil column or oil ammonia column by the method for alumina sol (Alumina gel) progress drips ball forming in step
Shaping.During drips ball forming, the concentration of alumina sol is preferably controlled as 15~23 mass % (in terms of alumina content), and Alumina gel is dense
Height is spent, viscosity is also high, and the slurries that are flowed out from pin hole are not easy to break into drop when dripping ball, preferably deforms as aspherical, very
To there is bracing wire phenomenon；Alumina gel concentration is too low, and viscosity is also low, and slurry droplet is easily broken without balling-up when falling into oil.
The inventive method (2) step is to carry out the wet bulb after shaping to be calcined obtained ball type carrier, and roasting is divided into two sections, one section
Roasting forms macropore, and two-stage calcination forms θ-aluminum oxide.Preferably 1~20 hour two-stage roasting time.Resulting vehicle is oxidation
Alumina supporter or the alumina support containing modified metal, wherein the method that the alumina support of the component containing modified metal can also use dipping
Prepare, i.e., the compound of the modified metal component of above-mentioned stanniferous, germanium, lead, indium, gallium or thallium is configured to maceration extract, uses maceration extract
Impregnate alumina support made from (2) step, by solid after dipping it is dry, be calcined and produce the carrying alumina of the component containing modified metal
Body.
When expanding agent used in (1) step is C10~C16Hydrocarbon when, after drips ball forming, after (2) step carries out one section of roasting, use
The air-treatment of moisture vapor 1~15 hour, the water content in air of processing is preferably 4~30 mass %, more preferably 4~20 matter
% is measured, treatment temperature is preferably identical with one section of sintering temperature.
After alumina support load active component provided by the invention, catalyst for dehydrogenation of low-carbon paraffin is can be made into, preparation is urged
The method of agent preferably includes：The alumina support of the above-mentioned component containing modified metal is used and contains VIII race's metal and halogen-containing chemical combination
The solution dipping of thing, is dried, 400~650 DEG C of roastings, then is impregnated with the water soluble compound solution of the metal of race containing IA, is dried,
400~650 DEG C of roastings.
In above-mentioned method for preparing catalyst, when VIII race's metal and halogen are introduced into carrier, containing used in maceration extract is prepared
The preferred chloroplatinic acid of compound or ammonium chloroplatinate of VIII race's metal.To be evenly distributed in the carrier VIII race's metal, in the leaching of preparation
Halogen-containing compound is added in stain liquid, to form competitive Adsorption.The halogen-containing compound preferably three added into maceration extract
Monoxone or hydrogen chloride, more preferably hydrogen chloride.
When IA race's metals are introduced into carrier, the preferred hydrogen of water soluble compound of the metal of race containing IA used in maceration extract is prepared
Potassium oxide, potassium nitrate or potassium chloride.
In the above method, when introducing active component by impregnating, preferably 20~70 DEG C of dipping temperature.During dipping maceration extract with
The liquid/solid ratio of carrier is 1.0~2.0ml/g, and after introducing active component after dipping every time, gained solid is both needed to dry, is calcined, and does
Preferably 100~300 DEG C of dry temperature, preferably 500~630 DEG C of sintering temperature.
In catalyst prepared by the above method, VIII race's tenor preferably 0.1 for being calculated on the basis of butt aluminum oxide~
1.0 mass %, the second metal component content preferably 0.1~1.0 mass %, IA race tenor preferably 0.5~2.0 mass %,
Content of halogen preferably 0.3~3.0 mass %.
The VIII preferred platinum of race's metal in the catalyst, the preferred potassium of IA races metal, the preferred tin of the second metal component, halogen are excellent
Select chlorine.
Catalyst prepared by the above method the preferred hydrogen of the gas for reduction, can also use using preceding needing to reduce
CO or other reducibility gas.Preferably 500~650 DEG C of reduction temperature, preferably 0.5~10 hour recovery time.Reduction can urge
Agent is carried out before loading reactor, can also be carried out after catalyst loads reactor before dehydrogenation reaction.
The catalyst is applied to the reaction of manufacturing olefin by low-carbon alkane dehydrogenation.By low-carbon alkanes in presence of hydrogen with low-carbon
Alkane dehydrogenating catalyst is at 400~800 DEG C, preferably 550~650 DEG C, and 0.1~1.0MPa of pressure, preferably 0.1~0.5MPa are (absolutely
Pressure) under conditions of react.
In course of reaction, the suitable mass space velocity that low-carbon alkanes contact with catalyst is 0.1~20h-1, more preferably 0.5
~10h-1。
Above-mentioned dehydrogenation reaction also can be selected vapor, argon, methane, ethane, carbon dioxide, nitrogen etc. as diluted material with
Low-carbon alkanes mixing is passed through reactor, and preferable diluted material is hydrogen.When selecting hydrogen, the mol ratio of hydrogen and low-carbon alkanes
It is preferred that 0.1~10：1st, more preferably 0.3~3：1.
Above-mentioned low-carbon alkanes are propane, butane or pentane, and described butane is normal butane, iso-butane.Reaction is preferable low
Carbon alkane is propane or iso-butane.
The present invention is further described below by example, but the present invention is not limited thereto.
Example 1
27g aluminium flakes are taken, the hydrochloric acid solution that 610 grams of concentration are 18 mass % is added, dissolves aluminium flake, obtain alchlor and contain
To measure as 4 mass % solution, be transferred to neutralizing tank, the ammoniacal liquor that the concentration for adding 850 grams is 6 mass %, 60 DEG C are well mixed,
PH value is 7.5~8.5.The aluminium hydroxide of generation is filtered, washing, and it is 1 that 9mL volume ratios are added in filter cake：1 nitric acid acid
Change, stir the lower solution for adding 40mL containing 30 grams of ureas and the hydrochloric acid solution containing 32 grams of stannous chlorides, make the amount containing Sn in solution be
The 0.32% of butt quality of alumina, stir 1 hour and be acidified, then add 30 grams of kerosene and 3 grams of NPEs stir
Mix 1 hour, with Al in colloidal sol2O3The solid content of meter is 20 mass %.By this colloidal sol instillation upper strata be oil phase, lower floor be ammoniacal liquor phase
Oil ammonia column in drips ball forming.Described oil phase is kerosene, and the concentration of ammoniacal liquor is 8 mass % in ammoniacal liquor phase.Wet bulb is in ammoniacal liquor phase
Middle 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 in air stream
Carry out one section to be calcined 4 hours, then handle 10 hours, be warming up in the air that vapour content is 5 volume % at 650 DEG C
1000 DEG C carry out two-stage calcination 4 hours, and stanniferous θ-Al are made2O3Carrier a, its physical property are shown in Table 1.
Example 2
Alumina support is prepared by the method for example 1, the difference is that taking (the German Sasol companies life of 132 grams of aluminium hydrate powders
Production, trade mark SB, alumina content is quality 76%), 100mL deionized waters are added, stirring makes its pulp in 1 hour, adds 9mL
Volume ratio is 1：Alumina gel, obtained stanniferous θ-Al is made in 1 nitric acid acidifying2O3Carrier b physical property is shown in Table 1.
Example 3
Alumina support is prepared by the method for example 1, the difference is that under agitation, adding and containing into the colloidal sol after acidifying
The aqueous solution of 40g ammonium hydrogen carbonate, and kerosene and NPE are added without, obtained stanniferous θ-Al2O3Carrier c's
Physical property is shown in Table 1.
Example 4
Alumina support is prepared by the method for example 1, the difference is that adding 40 grams of kerosene and 4 in the Alumina gel after acidifying
Gram AEO, obtained stanniferous θ-Al2O3Carrier d physical property is shown in Table 1.
Example 5
Alumina support is prepared by the method for example 1, the difference is that adding 15 grams of kerosene and 2 grams in the colloidal sol after acidifying
AEO, obtained stanniferous θ-Al2O3Carrier e physical property is shown in Table 1.
Example 6
Alumina support is prepared by the method for example 1, the difference is that adding urea not into the Alumina gel after acidifying and containing 32
The hydrochloric acid solution of gram stannous chloride, θ-Al are made2O3Carrier h, physical property are shown in Table 1.
Take above-mentioned not stanniferous θ-Al2O3Carrier h, impregnated 4 hours in 25 DEG C with the hydrochloric acid solution of chloride containing stannous, dipping
Tin (relative to butt aluminum oxide) containing 0.32 mass % in liquid, liquid/solid ratio is 1.8mL/g.Gained solid is in 120 after dipping
DEG C dry 12 hours, 500 DEG C of roasting 4h, stanniferous θ-Al are made2O3Carrier h'.
Example 7
Alumina support is prepared by the method for example 1, the difference is that not having to after one section of roasting at the air of moisture vapor
Carrier is managed, but directly carries out two-stage calcination, obtained stanniferous θ-Al2O3Carrier j physical property is shown in Table 1.
Comparative example 1
Alumina support is prepared by the method for example 1, the difference is that small in 650 DEG C of roastings 4 after alumina globule is dried
When, obtained stanniferous γ-Al2O3Carrier f physical property is shown in Table 1.
Comparative example 2
Alumina support is prepared by the method for example 1, the difference is that adding kerosene and nonyl not into the Alumina gel of acidifying
Phenol polyethenoxy ether, and after aluminum oxide is carried out into one section of roasting, directly carry out two-stage calcination, obtained stanniferous θ-Al2O3
Carrier g physical property is shown in Table 1.
Example 8
Prepare catalyst for dehydrogenation of low-carbon paraffin.
Stanniferous alumina globule carrier made from above-mentioned each example and comparative example is taken respectively, with the leaching containing chloroplatinic acid and hydrochloric acid
Stain liquid is impregnated 4 hours in 25 DEG C, and 0.30% platinum, 2.0% chlorine (both with respect to butt quality of alumina) are contained in maceration extract,
Liquid/solid ratio is 1.8mL/g.Solid is dried 12 hours in 120 DEG C after dipping, 500 DEG C of roasting 4h.Solid after roasting is used again
The mass % containing potassium 1.0 (relative to butt quality of alumina) potassium nitrate solution impregnates 4 hours in 25 DEG C, and liquid/solid ratio is
1.4mL/g.Solid is dried 12 hours in 120 DEG C after dipping, 600 DEG C of roasting 4h.By after roasting gained oxidized catalyst in
550 DEG C with hydrogen reducing 2 hours, obtain dehydrogenation.The platinum content calculated in catalyst on the basis of butt aluminum oxide is
0.30 mass %, Theil indices are 0.32 mass %, potassium content is 1.0 mass %, chlorinity is 1.0 mass %.
Obtained catalyst is represented 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, such as 2~10nm tables
Show 2nm<Diameter≤10nm hole.
Example 9~17
Following instance evaluates the reactivity worth of dehydrogenation.
In micro-reactor, load 6 milliliters of catalyst, using the mixed gas of hydrogen and propane as raw material, the purity of propane
More than 99.9%, 620 DEG C, 0.21MPa (absolute pressure), propane feed mass space velocity be 3.5h-1, hydrogen/propane mol ratio
For 0.5：Reacted under conditions of 1, chromatography is once carried out every sampling in 1 hour.Each catalyst in the differential responses time third
Alkane conversion ratio and Propylene Selectivity are shown in Table 2.
Table 2
As shown in Table 2, had more than the catalyst prepared by comparative example carrier by catalyst prepared by carrier of the present invention
High conversion of propane, react 50 hours, the selectivity of propylene is more than 95%, and the stability of catalyst is also preferable.It is small to react 50
When catalyst total carbon deposition it is low, there is good reactivity worth.
Claims (9)
1. a kind of θ-alumina support, there is 50~130m2/ g specific surface area, 0.5~1.0mL/g total pore volume, in carrier
The pore volume in a diameter of 2~10 nanometers of hole accounts for the 4~15% of total pore volume, the pore volume in a diameter of 10~20 nanometers of hole accounts for
The 40~60% of total pore volume, it is big that the pore volume in a diameter of 20~50 nanometers of hole accounts for the 1.0~5.0% of total pore volume, diameter
The pore volume of macropore in 50 nanometers but no more than 10 microns accounts for the 20~50% of total pore volume.
2. according to the carrier described in claim 1, it is characterised in that a diameter of 2~10 nanometers of hole in described alumina support
Pore volume account for the 7~15% of total pore volume, the pore volume in a diameter of 10~20 nanometers of hole account for total pore volume 43~60%,
It is more than 50 nanometers but micro- no more than 10 that the pore volume in a diameter of 20~50 nanometers of hole accounts for the 1.0~5.0% of total pore volume, diameter
The pore volume of the macropore of rice accounts for the 22~48% of total pore volume.
3. according to the carrier described in claim 1 or 2, it is characterised in that in the carrier contain selected from tin, germanium, lead, indium, gallium or
The modified metal component of thallium, the modified metal constituent content are calculated as 0.1~2.0 matter on the basis of butt alumina support
Measure %.
4. the preparation method of alumina support, comprises the following steps described in a kind of claim 1：
(1) sour peptization is added in aluminium hydroxide, alumina sol is made, adds expanding agent in alumina sol, drop ball into
Type, described expanding agent are C10~C16Hydrocarbon, urea or ammonium carbonate salts, the oxidation contained in the expanding agent and Alumina gel of addition
The mass ratio of aluminium is 0.05~0.6,
(2) after the wet bulb after (1) step drips ball forming is dried, one section of roasting is carried out in 620~680 DEG C, then it is warming up to 900~
1100 DEG C carry out two-stage calcination and carrier are made.
5. in accordance with the method for claim 4, it is characterised in that described C10~C16Hydrocarbon be kerosene, ammonium carbonate salts are carbonic acid
Hydrogen ammonium or ammonium carbonate.
6. in accordance with the method for claim 4, it is characterised in that when expanding agent used is C10~C16Hydrocarbon when, drips ball forming
Afterwards, 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 processing is 4
~30 mass %.
7. in accordance with the method for claim 4, it is characterised in that in alumina sol made from (1) step add selected from tin,
Germanium, lead, indium, gallium or thallium modified metal component compound.
8. in accordance with the method for claim 7, it is characterised in that the compound of the modified metal component is the metal group
Chloride, nitrate or the organic compound divided.
9. in accordance with the method for claim 7, it is characterised in that the compound of the modified metal component is stannous bromide, chlorine
Change stannous, butter of tin, butter of tin pentahydrate or tetrabutyltin.
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| 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 |
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