CN104289218B - Catalyst for preparing isobutene from isobutane through dehydrogenation - Google Patents
Catalyst for preparing isobutene from isobutane through dehydrogenation Download PDFInfo
- Publication number
- CN104289218B CN104289218B CN201310300752.5A CN201310300752A CN104289218B CN 104289218 B CN104289218 B CN 104289218B CN 201310300752 A CN201310300752 A CN 201310300752A CN 104289218 B CN104289218 B CN 104289218B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- slaine
- dehydrogenation
- weight contents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing isobutene from isobutane through dehydrogenation. The catalyst is prepared through following steps: adding a metal salt solution to a slurry liquid containing an inorganic supporter under ultrasonic wave; adding a solution containing a reduction agent to the slurry liquid under protection of an inert gas; and finally performing solid-liquid separation to obtain the catalyst. Metals in the metal salt include Pt, Sn and K. The catalyst is high in metal dispersing degree, is uniform in distribution of active centre component granularity, is small in particle size, is low in preparation cost and is high in catalytic activity when being used for preparing the isobutene from isobutane through dehydrogenation.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane.The present invention is also related to
And the application of above-mentioned catalyst.
Background technology
Isobutene. is a kind of very important Organic Chemicals, and its demand remains that what is increased becomes in the world
Gesture, it may not only be applied to produce the elastomers such as isoprene rubber, butyl rubber, polyisobutylene, can be used to make gasoline and lubricating oil
Additive, and also act as the raw material of other fine chemical products, such as resist by made by isobutene. is with phenol or cresol
Oxygen agent is the main auxiliary agent of the chemical products such as plastics；Octyl phenol by isobutene dimer and phenol synthesis is manufacture rubber industry
Vulcanization accelerator necessary to raw material；The methacrylic acid produced by isobutene.（MAA）Methacrylic acid is obtained Jing after esterification
Methyl ester is the monomer of lucite, for producing various polymer and copolymer etc..Isobutene. has become the whole world most at present
One of popular fine chemical product, and there is very big breach in the supply of isobutene..Increase and potentiality in isobutene. production line
Maximum is dehydrogenation of isobutane.
According to reported in literature, the catalyst system employed in dehydrogenation of isobutane technique, mainly there are two classes：One class is oxide
Type, with Cr2O3Based on, in Catofin techniques, the Cr/Al Catalyst Conversions for adopting for 60-61%, selectivity 91-93%.
In Linele techniques, the Cr/Al Catalyst Conversions for adopting for 40-45%, selectivity 91-95%.One class is metal catalyst.
Mainly Pt/Al2O3It is noble metal catalyst, the such catalyst employed in Oleflex techniques, conversion ratio is 45-55%, choosing
Selecting property 91-93%.
At present, traditional preparation method for preparing load type metal nanocatalyst mainly have infusion process, coprecipitation, from
Sub- exchange process and precipitation reducing process.The active component of loaded catalyst prepared by traditional preparation method often skewness
Even, metal dispersity is low, and content of metal is big, and production cost is high.
The content of the invention
For deficiency of the prior art, the invention provides a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane, overcomes
Conventional impregnation method prepares the shortcoming of load type metal catalyst, active component ion epigranular, narrow diameter distribution, catalysis
The high advantage of activity.
According to an aspect of the invention, there is provided a kind of preparing isobutene through dehydrogenation of iso-butane catalyst, which passes through to include
It is prepared by the method for following steps：Under ul-trasonic irradiation, metal salt solution is added in the serosity containing inorganic carrier, Ran Hou
To be added in the serosity containing the solution of reducing agent under the protection of noble gases, most after Jing solid-liquid separation, obtain described urging
Agent, wherein the metallic element in the slaine is Pt, Sn and K.
The catalyst provided by the present invention, its preparation method is simple, low cost.Wherein, the utilization of the ultrasound wave, has
Beneficial in catalyst active metallic element it is dispersed.The catalyst provided by the present invention, active metallic element（Such as Pt,
Sn and K）Dispersion is high, active center even particle size distribution, and particle diameter is little and the advantages of high catalysis activity.
In above-mentioned catalyst, Pt weight contents in the catalyst are：0.1-1%, preferred 0.4-0.6%, Sn exist
Weight content in catalyst：0.1-2%, preferred 1-1.5%, K weight content in the catalyst is：0.1-2%, preferred 0.5-
1.5%。
In above-mentioned catalyst, the slaine can be any suitable salt containing Pt, Sn and K.It is concrete at one
In embodiment, inorganic salt of the slaine for Pt, Sn and K.Sn inorganic salts such as butter of tin, stannum dichloride etc..Potassium inorganic salt
Such as potassium nitrate and potassium chloride etc..In a preferred embodiment, the slaine is chloroplatinic acid, butter of tin and potassium chloride.
In a specific embodiment of above-mentioned catalyst, the frequency of the ultrasound wave is 40-120KHz.In the frequency
It is interior, be conducive to dispersion and the active center even particle size distribution of active metallic element in final catalyst, be conducive to improving
The activity of catalyst.
In one embodiment of above-mentioned catalyst, alcoholic solution of the metal salt solution for slaine, such as slaine
Methanol solution or ethanol solution, the ethanol solution of preferred slaine.
In above-mentioned catalyst, the inorganic carrier is any suitable carrier.In a specific embodiment, the nothing
Airborne body is selected from molecular sieve, silicon oxide and aluminium oxide, preferred aluminium oxide.
In above-mentioned catalyst, the use of the noble gases is conducive to the carrying out of reduction reaction.In an instantiation
In, the noble gases are selected from nitrogen, helium and argon, preferred nitrogen.
In above-mentioned catalyst, the solution containing the reducing agent preferably alkaline solution containing reducing agent.The reducing agent is excellent
Choosing is selected from formaldehyde, paraformaldehyde, hydrazine hydrate and sodium borohydride.
In a specific embodiment of said method, under ul-trasonic irradiation, by metal salt solution（The alcohol of slaine is molten
Liquid）It is added in the serosity containing inorganic carrier of stirring, then adds containing also in the serosity under the protection of noble gases
The solution of former agent（Such as alkaline solution of the Deca containing reducing agent）, Jing solid-liquid separation（Such as centrifugation）, described catalyst is obtained,
Metallic element in wherein described slaine is Pt, Sn and K.In an instantiation, precipitation after solid-liquid separation is scrubbed,
It is dried and roasting, obtains the catalyst.
In another specific embodiment of above-mentioned catalyst, methods described is carried out at 20-100 DEG C, such as at 20-80 DEG C
At a temperature of carry out.In a specific example, the ultrasound wave is produced by supersonic generator, the supersonic generator
The temperature of interior water-bath is 20-100 DEG C.
A specific embodiment of the invention, under conditions of supersonic induced, with such as dosing pump or peristaltic pump（Flow
Such as it is 0.1-10ml/min）Metal salt solution and reducing agent are distributed in the mixture slurry solution being made up of carrier material, are made
Metal ion absorbing and reducing on carrier surface, is then centrifuged for separating, and the precipitation for obtaining such as is washed with deionized, be dried, into
Type and roasting, obtain described catalyst, i.e. support type Pt systems metal nano catalyst.
In an instantiation of the catalyst of the present invention, before for dehydrogenation of isobutane reaction, the catalyst is needed
Reduced with hydrogen, made platinum-group transition element reduction.In a specific embodiment, reduction temperature is 300-600 DEG C, when
Between 1-5h, catalyst after carrying out reduction can be used for catalytic reaction.
According to a further aspect in the invention, there is provided a kind of method of preparing isobutene through dehydrogenation of iso-butane, the iso-butane exist
Reacted in the presence of above-mentioned catalyst, obtained isobutene..
In a specific embodiment of said method, the reaction temperature of the reaction is 500～700 DEG C, reaction pressure
For normal pressure to 1Mpa, air speed is 500-2000h-1。
According to the catalyst that the present invention is provided, using Pt, Sn and K as active metal component, the catalysis of support type is obtained
Agent, the dispersion of active metal component are high, and active center component particle size is evenly distributed, and particle diameter is little, low cost of manufacture；Urge described
Agent is used for preparing isobutene through dehydrogenation of iso-butane, has the advantages that catalysis activity is high.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but does not constitute any limitation of the invention
Embodiment 1：
Weighed the γ-Al of 10g2O3In adding flask, 50ml deionized waters are subsequently adding, flask is fixed on into ultrasound
In the tank of wave producer, and agitator is installed.The tank temperature setting of supersonic generator is 60 DEG C, and stir speed (S.S.) is set to
500 turns/min, start supersonic generator, setting tranmitting frequency is 60 KHz.By the chloroplatinic acid weighed and butter of tin
It is transferred in flask with potassium chloride, adds 10ml dehydrated alcohol which is fully dissolved.With peristaltic pump with the speed of 1ml/min by nothing
The alcohol hydrochloric acid solution of machine salt is added drop-wise in mixed serum, after inorganic salt solution is all added, continues stirring serosity 10min.
It is passed through high-purity N2Purging 30min removes the oxygen of dissolving.Then 10ml paraformaldehydes (01mol/L) and Na are slowly added dropwise2CO3
(005mol/L) alkaline solution, is passed through high-purity N2Protection, condensing reflux simultaneously stir 2.5h to ensure to reduce completely.Then close
Supersonic generator and agitator are closed, while hot sucking filtration reduzate after being washed with deionized 3 times, are dried 8 hours at 80 DEG C,
600 DEG C of roasting 5h in Muffle furnace, had both obtained catalyst A.The mass content of each component is respectively：Pt accounts for 0.5%, Sn and accounts for 1.5%, K
Account for 1%.
The catalyst A of preparation is carried out into iso-butane（i-C4H10）The measure of catalytic dehydrogenation activity, concretely comprises the following steps：Before reaction
Catalyst is reduced in a hydrogen atmosphere, i.e., the hydrogen reducing 2h at 500 DEG C.Reactor feed gas are constituted：H2：i-C4H10=1:1；Always
Air speed：2000h-1；Reaction stagnation pressure：0.1MPa；Reaction temperature；560℃.Reaction result is shown in Table 1
Embodiment 2：
With embodiment 1, difference is, Deca 10ml formaldehyde (0.1mol/L) and Na2CO3(005mol/L) alkali
Property solution.Data are shown in Table 1.
Embodiment 3：
With embodiment 1, difference is, the alkali of Deca 10ml hydrazine hydrate (0.1mol/L) and NaOH (01mol/L)
Property solution.Data are shown in Table 1.
Embodiment 4：
With embodiment 1, difference is, Deca 10ml sodium borohydride (0.1mol/L) and NaOH's (01mol/L)
Alkaline solution.Data are shown in Table 1.
Embodiment 5：
With embodiment 1, difference is that Pt accounts for 0.4%, Sn and accounts for 1%, K and accounts for 0.8% in catalyst.Data are shown in Table 1.
Embodiment 6
With embodiment 1, difference is that Pt accounts for 0.6%, Sn and accounts for 1.5%, K and accounts for 1.5% in catalyst.Data are shown in Table 1.
Comparative example 1：
With embodiment 1, difference is not add paraformaldehyde and Na2CO3Alkaline solution；Work as inorganic salt solution
After all adding, continue stirring serosity 2.5h；It is then shut off supersonic generator and agitator.Data are shown in Table 1.
Comparative example 2：
The chloroplatinic acid weighed and butter of tin and potassium chloride are transferred in beaker, add 10ml dehydrated alcohol to fill which
Divide dissolving.Weighed the γ-Al of 10g2O3In adding beaker, it is sufficiently stirred for, dries 8 hours at 80 DEG C, 600 in Muffle furnace
DEG C roasting 5h,.The mass content of each component is respectively：Pt accounts for 0.5%, Sn and accounts for 1.5%, K and accounts for 1%.
The catalyst F of preparation is carried out into iso-butane（i-C4H10）The measure of catalytic dehydrogenation activity, concretely comprises the following steps：Before reaction
Catalyst is reduced in a hydrogen atmosphere, i.e., the hydrogen reducing 2h at 500 DEG C.Reactor feed gas are constituted：H2：i-C4H10=1:1；Always
Air speed：2000h-1；Reaction stagnation pressure：0.1MPa；Reaction temperature；560℃.Data are shown in Table 1.
Table 1
From table 1 it follows that the catalyst provided according to the present invention, its catalysis activity is significantly improved, with higher
Iso-butane conversion ratio, selective isobutene and isobutene. yield.Meanwhile, according to the catalyst that the present invention is provided, its stability is high,
After operation a period of time, still with higher catalysis activity.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be made by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in which is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this
It is bright to can be extended to other all methods and applications with identical function.
Claims (17)
1. a kind of preparation method of preparing isobutene through dehydrogenation of iso-butane catalyst, which comprises the steps of：Under ul-trasonic irradiation,
Metal salt solution is added in the serosity containing inorganic carrier, then the solution containing reducing agent is added under the protection of noble gases
Enter in the serosity, most after Jing solid-liquid separation, the precipitate with deionized water washing for obtaining is dried, molding and roasting, obtains institute
The catalyst stated, wherein the metallic element in the slaine is Pt, Sn and K, K weight contents in the catalyst are
0.8-2%.
2. method according to claim 1, it is characterised in that Pt weight contents in the catalyst are 0.1-1%；
Sn weight contents in the catalyst are 0.1-2%；K weight contents in the catalyst are 0.8-2%.
3. method according to claim 2, it is characterised in that Pt weight contents in the catalyst are 0.4-
0.6%；Sn weight contents in the catalyst are 1-1.5%；K weight contents in the catalyst are 1-1.5%.
4. the method according to any one in claims 1 to 3, it is characterised in that the slaine is Pt, Sn and K
Inorganic salt.
5. method according to claim 4, it is characterised in that the slaine is chloroplatinic acid, butter of tin and potassium chloride.
6. the method according to any one in claims 1 to 3, it is characterised in that the frequency of the ultrasound wave is 40-
120KHz。
7. the method according to any one in claims 1 to 3, it is characterised in that the metal salt solution is slaine
Alcoholic solution.
8. method according to claim 7, it is characterised in that ethanol solution of the metal salt solution for slaine.
9. the method according to any one in claims 1 to 3, it is characterised in that the inorganic carrier selected from molecular sieve,
Silicon oxide and aluminium oxide.
10. method according to claim 9, it is characterised in that the inorganic carrier is aluminium oxide.
11. methods according to any one in claims 1 to 3, it is characterised in that the noble gases selected from nitrogen,
Helium and argon.
12. methods according to claim 11, it is characterised in that the noble gases are nitrogen.
13. methods according to any one in claims 1 to 3, it is characterised in that the solution containing reducing agent be containing
The alkaline solution of reducing agent.
14. methods according to claim 13, it is characterised in that the reducing agent is selected from formaldehyde, paraformaldehyde, hydrazine hydrate
And sodium borohydride.
15. methods according to any one in claims 1 to 3, it is characterised in that methods described is entered at 20-100 DEG C
OK.
A kind of 16. methods of preparing isobutene through dehydrogenation of iso-butane, iso-butane side described in any one in claim 1～15
Reacted in the presence of catalyst prepared by method, obtained isobutene..
17. methods according to claim 16, it is characterised in that the reaction temperature of the reaction is 500-700 DEG C, reaction
Pressure is normal pressure to 1Mpa, and volume space velocity is 500-2000h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300752.5A CN104289218B (en) | 2013-07-17 | 2013-07-17 | Catalyst for preparing isobutene from isobutane through dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300752.5A CN104289218B (en) | 2013-07-17 | 2013-07-17 | Catalyst for preparing isobutene from isobutane through dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104289218A CN104289218A (en) | 2015-01-21 |
| CN104289218B true CN104289218B (en) | 2017-04-26 |
Family
ID=52309305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310300752.5A Active CN104289218B (en) | 2013-07-17 | 2013-07-17 | Catalyst for preparing isobutene from isobutane through dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104289218B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10981149B2 (en) | 2019-03-18 | 2021-04-20 | Uop Llc | Dehydrogenation catalyst with optimum modifier profile index |
| WO2022018081A1 (en) | 2020-07-21 | 2022-01-27 | Basf Se | A zeolite catalyst and use thereof for the dehydrogenation of alkanes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766266A (en) * | 1985-11-13 | 1988-08-23 | Arco Chemical Company | Dehydrogenation of isobutane |
| US5736478A (en) * | 1995-03-24 | 1998-04-07 | Wisconsin Alumni Research Foundation | Catalyst to dehydrogenate paraffin hydrocarbons |
| CN100496700C (en) * | 2007-07-13 | 2009-06-10 | 北京工业大学 | Method for preparation of load type nano metallic catalyst |
| CN101862669B (en) * | 2010-06-23 | 2012-06-20 | 东南大学 | Catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN102909092B (en) * | 2011-08-01 | 2015-04-01 | 中国石油化工股份有限公司 | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction |
-
2013
- 2013-07-17 CN CN201310300752.5A patent/CN104289218B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Novel Coated Pt@SnO2/Al2O3 Catalyst for Propane Dehydrogenation;Li Jun等;《Rare Metal Materials and Engineering》;20130228;第42卷(第2期);第259-262页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104289218A (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108620092B (en) | Alumina-supported PtCu monatomic alloy catalyst and preparation method and application thereof | |
| CN1130265C (en) | Catalyst capable of using on carrier in organic compound conversion reaction | |
| CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
| CN102218291B (en) | Chemical reaction method | |
| CN103084169B (en) | A kind of hydrogenation of unsaturated hydrocarbons Catalysts and its preparation method and application | |
| CN104418371B (en) | A kind of preparation method of ball-aluminium oxide | |
| CN107537481A (en) | The monatomic rhodium base catalyst of support type and its applied in hydroformylation of olefin | |
| CN104356258B (en) | Preparation method of rare earth element modified and aldehyde removed resin and application of rare earth element modified and aldehyde removed resin in ethylene glycol refining | |
| CN113145178B (en) | Janus structure polymer-based nano metal catalyst and preparation method and application thereof | |
| CN104289218B (en) | Catalyst for preparing isobutene from isobutane through dehydrogenation | |
| CN109806885A (en) | A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection | |
| CN108250069A (en) | A kind of preparation method of isooctyl acid | |
| CN104437654A (en) | Vinyl acetate catalyst and preparation method thereof | |
| CN105001357A (en) | Continuous preparation method for catalytically synthesizing polyvinyl butyral resin through organic acid | |
| CN109569589A (en) | A kind of levulic acid adds hydrogen gamma-valerolactone M-B@Al2O3Catalyst and its preparation method and application | |
| CN107008223B (en) | The adsorbent and preparation method thereof of low-load amount high dispersive type benzene refining desulfurization | |
| CN105797719A (en) | Load type duplex metal/multi-metal catalyst for hydrogenation synthesis of metanilic acid from m-Nitrobenzenesulfonic acid and preparation method and application | |
| CN109317178A (en) | A kind of loaded catalyst and preparation method thereof adding hydrogen preparation hydrogenated styrene-butadiene rubber for heterogeneous solution | |
| CN110508277A (en) | A kind of high dispersive palladium nanoparticle catalyst and its preparation method and application | |
| CN111389398B (en) | Preparation method of hierarchical hollow silica confinement cuprous oxide visible-light-driven photocatalyst | |
| CN105080603B (en) | Catalyst for aniline preparation by selective hydrogenation of nitrobenzene as well as preparation method and application method of catalyst | |
| CN104923222A (en) | Preparation method of catalyst for cyclohexene prepared by selective benzene hydrogenation, and catalyst prepared by method | |
| CN102229587B (en) | Method for generating succinic anhydride through maleic anhydride hydrogenation catalyzed by Nano-Ni | |
| CN104841429B (en) | A kind of synthesising gas systeming carbinol carried copper-base catalyst and preparation method thereof | |
| CN105732284A (en) | Selective hydrogenation method for C3 fraction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |