CN105214657A - A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof - Google Patents
A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof Download PDFInfo
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Abstract
A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, comprise alumina support and take carrier as the following active component of the content of benchmark: VIII race's metal 0.1 ~ 2.0 quality %, second metal component 0.1 ~ 2.0 quality %, IA race metal 0.5 ~ 5.0 quality %, halogen 0.3 ~ 10.0 quality %, in described alumina support, diameter is that the hole of 2 ~ 10 nanometers accounts for 4 ~ 15% of total pore volume, diameter is that the hole of 10 ~ 20 nanometers accounts for 40 ~ 60% of total pore volume, diameter is that the hole of 20 ~ 50 nanometers accounts for 1.0 ~ 5.0% of total pore volume, diameter is greater than 50 nanometers but the macropore being not more than 10 microns accounts for 20 ~ 50% of total pore volume, the second described metal component is selected from tin, germanium, plumbous, indium, gallium or thallium.This catalyst is used for preparing propylene by dehydrogenating propane, have higher activity and selectivity, and coke deposit rate is low.
Description
Technical field
The present invention is a kind of dehydrating alkanes alkene catalyst and preparation method thereof, specifically, is a kind of Catalysts and its preparation method of lower alkanes Oxidative Dehydrogenation alkene.
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 catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof, this catalyst is used for manufacturing olefin by low-carbon alkane dehydrogenation, have higher activity and selectivity, and coke deposit rate is low.
Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation provided by the invention, comprises alumina support and take carrier as the following active component of the content of benchmark:
In described alumina support 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 second described metal component is selected from tin, germanium, lead, indium, gallium or thallium.
Catalyst of 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 catalyst support 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 allocation proportion of macropore obviously increases, and in middle pore size distribution, larger proportion is occupied in the hole of 10 ~ 20nm.The catalyst obtained by this carrier, mesopore is wherein conducive to the dehydrogenation reaction of low-carbon alkanes, and macropore is conducive to the diffusion in the catalyst of low-carbon alkanes gas, and makes catalyst have the ability of higher accommodation carbon deposit, and anti-carbon deposition ability improves.This catalyst has higher conversion of propane and Propylene Selectivity, the good stability of catalyst when being used for propane catalytic dehydrogenating reaction, and has good regenerability.
Catalyst of the present invention alumina support used 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.For using moving-burden bed reactor in course of reaction, continuous catalyst regenerating need be carried out, preferably use ball type carrier, 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.
VIII race's tenor described in catalyst of the present invention is preferably 0.1 ~ 1.0 quality %, the second metal component content is preferably 0.1 ~ 1.0 quality %, IA race tenor is preferably 0.5 ~ 2.0 quality %, content of halogen is preferably 0.3 ~ 3.0 quality %.
The described preferred platinum of VIII race's metal, the preferred potassium of IA race metal, the preferred tin of the second metal component, the preferred chlorine of halogen.
The specific area of described alumina support is 50 ~ 130m
2/ g, pore volume are 0.6 ~ 0.75 ml/g.Most probable pore size is 10 ~ 20nm.
The preparation method of catalyst provided by the invention, comprises the steps:
(1) in aluminium hydroxide, add sour peptization, obtained alumina sol, in alumina sol, add expanding agent and the compound containing the second metal component, drip 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,
(3) solution impregnation of the carrier (2) step obtained containing VIII race's metal and halogen-containing compound, dry, 400 ~ 650 DEG C of roastings,
(4) the water soluble compound solution impregnation of the carrier (3) step obtained containing IA race metal, dry, 400 ~ 650 DEG C of roastings.
In said method, (1) step for drip ball forming with alumina sol, the preferred C of expanding agent added in alumina sol (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 50 ~ 90 DEG C, preferably 60 ~ 80 DEG C, then filter, wash, in filter cake, 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, wherein also can add organic acid, as acetic acid or citric 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.After adding expanding agent, add containing the compound of the second metal component in Alumina gel, this compound is the chloride of the second metal component or organic compound preferably, preferred stannous bromide, stannous chloride, butter of tin, butter of tin pentahydrate or tetrabutyltin.
In said method, the described compound containing the second metal component can not add in (1) step, and after the compound wiring solution-forming containing the second metal component is flooded (2) one-step baking, carrier introduces the second metal component.
(1) method of in step, alumina sol being carried out dripping ball forming can be that hot forming oil column or oil ammonia column are shaping.
The inventive method (2) step is the wet bulb after shaping is carried out roasting prepare 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.
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, carry out steam treatment 1 ~ 15 hour with the air of moisture vapor, the water content in air of process is preferably 4 ~ 30 volume %, more preferably 4 ~ 20 volume %.Steam treatment temperature is preferably identical with one section of sintering temperature.
The inventive method (3) step, for introduce VIII race's metal and halogen in carrier, prepares the maceration extract preferred chloroplatinic acid of compound containing VIII race's metal 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.
The inventive method (4) step, for introduce IA race metal in carrier, prepares the maceration extract preferred potassium hydroxide of water soluble compound containing IA race metal used, potassium nitrate or potassium chloride.
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.
Catalyst of the present invention 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.
Catalyst of the present invention is applicable to the reaction of lower alkanes Oxidative Dehydrogenation alkene.By low-carbon alkanes in presence of hydrogen with catalyst of the present invention 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.
Low-carbon alkanes of the present invention 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
Prepare alumina support of the present invention.
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 %.Aluminum trichloride solution is proceeded to neutralizing tank, and add the ammoniacal liquor that 850 grams of concentration are 6 quality %, 60 DEG C mix, and pH value is 7.5 ~ 8.5.The aluminium hydroxide generated after filtration, washing, in filter cake, add 9mL volume ratio is that the nitric acid acidifying of 1:1 obtains colloidal sol.
In colloidal sol, add the hydrochloric acid solution that 40mL contains the solution of 30 grams of ureas and the stannous chloride containing 32 grams under stirring, make the 0.32 quality % being butt aluminium oxide containing Sn amount in solution, stir acidifying in 1 hour.Then under agitation in the colloidal sol of acidifying, 30 grams of kerosene and 3 grams of AEOs are dropwise added.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 76 quality %), 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
3carrier b, its physical property 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 100 grams of aqueous solution containing 40g carbonic hydroammonium, instead of add kerosene and AEO, 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 colloidal sol obtained 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 obtained in acidifying, obtained stanniferous θ-Al
2o
3the physical property of carrier e is in table 1.
Example 6 ~ 10
Prepare catalyst of the present invention.
Get above-mentioned stanniferous θ-Al respectively
2o
3bead, floods 4 hours in 25 DEG C with the maceration extract containing chloroplatinic acid and hydrochloric acid, containing the platinum of 0.30 quality %, the chlorine (all relative to butt aluminium oxide) of 2.0 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.Solid after roasting is flooded 4 hours in 25 DEG C with potassium nitrate solution again, containing potassium 1.0 quality % (relative to butt aluminium oxide) in potassium nitrate solution, Gu liquid/than being 1.4mL/g.After dipping, gained solid was in 120 DEG C of dryings 12 hours, 600 DEG C of roasting 4h.By gained catalyst after roasting in 550 DEG C with hydrogen reducing 2 hours, obtain catalyst A, B, C, D, E respectively.Catalyst numbering prepared by each example and with carrier be each constituent content of benchmark in table 2, lower with.
Example 11
(1) alumina support is prepared
Stanniferous θ-Al is prepared by the method for example 1
2o
3bead carrier is 0.30 quality % of butt aluminium oxide containing Sn amount in the tin chloride solution added in the colloidal sol unlike gained after acidifying, during two-stage calcination by alumina globule at 1100 DEG C of roasting 6h, obtained stanniferous θ-Al
2o
3the physical property of carrier f is in table 1.
(2) Kaolinite Preparation of Catalyst
Get carrier f, by the method Kaolinite Preparation of Catalyst of example 6, contain potassium 0.8 quality % unlike in potassium nitrate solution used during introducing potassium, each constituent content of obtained catalyst F is in table 2.
Example 12
(1) alumina support is prepared
Stanniferous θ-Al is prepared by the method for example 1
2o
3bead carrier is 0.19 quality % of butt aluminium oxide, obtained stanniferous θ-Al containing Sn amount in the tin chloride solution added in the colloidal sol unlike gained after acidifying
2o
3the physical property of carrier g is in table 1.
(2) Kaolinite Preparation of Catalyst
Get carrier g, by the method Kaolinite Preparation of Catalyst of example 6, each constituent content of obtained catalyst G is in table 2.
Example 13
(1) alumina support is prepared
Stanniferous θ-Al is prepared by the method for example 1
2o
3bead carrier is 0.16 quality % of butt aluminium oxide, obtained stanniferous θ-Al containing Sn amount in the tin chloride solution added in the colloidal sol unlike gained after acidifying
2o
3the physical property of carrier h is in table 1.
(2) Kaolinite Preparation of Catalyst
Get carrier h, by the method Kaolinite Preparation of Catalyst of example 6, each constituent content of obtained catalyst H is in table 2.
Example 14
Get stanniferous θ-Al prepared by example 1
2o
3bead carrier a, by the method Kaolinite Preparation of Catalyst of example 6, be potassium hydroxide solution unlike solution used during introducing potassium, containing potassium 1.2 quality %, each constituent content of obtained catalyst I is in table 2.
Example 15
(1) alumina support is prepared
Stanniferous θ-Al is prepared by the method for example 1
2o
3bead carrier, carries out one section of roasting after 4 hours unlike at 650 DEG C in air stream, no longer uses the air stream process of moisture vapor, but is directly warming up to 1000 DEG C and carries out two-stage calcination 4h, obtained stanniferous θ-Al
2o
3the physical property of carrier j is in table 1.
(2) Kaolinite Preparation of Catalyst
Get carrier j, by the method Kaolinite Preparation of Catalyst of example 6, each constituent content of obtained catalyst J is in table 2.
Comparative example 1
Stanniferous θ-Al is prepared by the method for example 1
2o
3bead carrier, unlike not adding kerosene and AEO in the colloidal sol after acidifying, and after dripping ball forming, gained wet bulb is after one section of roasting, and the air without moisture vapor carries out expanding treatment, obtained stanniferous θ-Al
2o
3carrier k, its physical property is in table 1.
Get carrier k, by the method load active component Kaolinite Preparation of Catalyst of example 6, each constituent content of obtained catalyst K is in table 2.
Comparative example 2
Stanniferous Al is prepared by the method for example 1
2o
3bead carrier, unlike after the alumina globule drying of dripping ball forming 650 DEG C of roastings 4 hours, obtained stanniferous γ-Al
2o
3carrier m, its physical property is in table 1.
Get carrier m, by the method load active component Kaolinite Preparation of Catalyst of example 6, each constituent content of obtained catalyst M is in table 2.
Example 16 ~ 27
In micro-reactor, load 2 milliliters of catalyst, with the mist of hydrogen and propane for raw material, 620 DEG C, 0.21MPa (absolute pressure), propane feed mass space velocity be 9.0h
-1, hydrogen/propane mol ratio be react 10 hours under the condition of 0.5:1, every 0.5 hour, sampling should be carried out carries out chromatography, calculates conversion of propane and Propylene Selectivity, the results are shown in Table 3.
As shown in Table 3, catalyst of the present invention, than comparative catalyst K and M, has higher conversion of propane, Propylene Selectivity is greater than 95 quality %, the stability of catalyst is also better, and the total carbon deposition quantity of catalyst of reaction in 10 hours is lower, illustrates that catalyst of the present invention has excellent reactivity worth.
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.
Table 2
Table 3
Claims (15)
1. a lower alkanes Oxidative Dehydrogenation alkene catalyst, comprises alumina support and take carrier as the following active component of the content of benchmark:
In described alumina support 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 second described metal component is selected from tin, germanium, lead, indium, gallium or thallium.
2. according to catalyst 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 catalyst described in claim 1 or 2, it is characterized in that described aluminium oxide is θ-aluminium oxide.
4., according to the catalyst described in claim 1 or 2, it is characterized in that VIII described race's tenor is 0.1 ~ 1.0 quality %, the second metal component content is 0.1 ~ 1.0 quality %, IA race tenor is 0.5 ~ 2.0 quality %, content of halogen is 0.3 ~ 3.0 quality %.
5., according to the catalyst described in claim 1 or 2, it is characterized in that VIII described race's metal is platinum, IA race metal is potassium, and halogen is chlorine.
6., according to catalyst according to claim 1, it is characterized in that the specific area of described alumina support is 50 ~ 130m
2/ g, pore volume are 0.6 ~ 0.75 ml/g.
7., according to catalyst according to claim 1, it is characterized in that described low-carbon alkanes is propane, butane or pentane.
8. a preparation method for catalyst described in claim 1, comprises the steps:
(1) in aluminium hydroxide, add sour peptization, obtained alumina sol, in alumina sol, add expanding agent and the compound containing the second metal component, drip 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,
(3) solution impregnation of the carrier (2) step obtained containing VIII race's metal and halogen-containing compound, dry, 400 ~ 650 DEG C of roastings,
(4) the water soluble compound solution impregnation of the carrier (3) step obtained containing IA race metal, dry, 400 ~ 650 DEG C of roastings.
9. in accordance with the method for claim 8, it is characterized in that the expanding agent described in (1) step is C
10~ C
16hydrocarbon, urea or ammonium carbonate salts.
10. in accordance with the method for claim 9, it is characterized in that described C
10~ C
16hydrocarbon be kerosene, ammonium carbonate salts is carbonic hydroammonium or ammonium carbonate.
11. in accordance with the method for claim 8, and it is characterized in that the expanding agent added in (1) step is is 0.1 ~ 0.5 with the mass ratio of aluminium oxide that contains in alumina sol.
12. in accordance with the method for claim 9, 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 2 ~ 30 volume %.
13. in accordance with the method for claim 8, it is characterized in that the compound do not added in the alumina sol described in (1) step containing the second metal component, and after the compound wiring solution-forming containing the second metal component is flooded (2) one-step baking, carrier introduces the second metal component.
14. in accordance with the method for claim 8, it is characterized in that the described compound containing the second metal component is its chloride or organic compound, water soluble compound containing IA race metal is potassium hydroxide, potassium nitrate or potassium chloride, compound containing VIII race's metal is chloroplatinic acid or ammonium chloroplatinate, and described halogen-containing compound is hydrogen chloride.
15. in accordance with the method for claim 14, it is characterized in that the described compound containing the second metal component is stannous bromide, stannous chloride, butter of tin, butter of tin pentahydrate or tetrabutyltin.
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| CN107879889A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method of dehydrogenating low-carbon alkane reaction |
| CN108014795A (en) * | 2016-11-04 | 2018-05-11 | 中国科学院大连化学物理研究所 | A kind of propane dehydrogenation catalyst and its preparation method and application |
| CN108295846A (en) * | 2018-02-11 | 2018-07-20 | 四川润和催化新材料股份有限公司 | A kind of alkane dehydrogenating catalyst and preparation method thereof |
| CN110975925A (en) * | 2019-12-04 | 2020-04-10 | 中国科学院上海高等研究院 | Gallium indium tin metal catalyst, preparation method and application |
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