CN105396583B - A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application - Google Patents
A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application Download PDFInfo
- Publication number
- CN105396583B CN105396583B CN201410461255.8A CN201410461255A CN105396583B CN 105396583 B CN105396583 B CN 105396583B CN 201410461255 A CN201410461255 A CN 201410461255A CN 105396583 B CN105396583 B CN 105396583B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- platinum
- tin
- propane
- preparing propylene
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application.The catalyst is using aluminium oxide as carrier, using platinum group metal as active component, using carbon and tin as auxiliary agent；On the basis of catalyst quality, platinum element mass percentage is 0.001~5%, and tin metal element mass percentage is 0.001%~5%, and carbon mass percentage is 0.001~1%.The preparation method of the catalyst is as follows：Dip loading active component and auxiliary agent on the alumina support first, then in H2And C2H4Mixed atmosphere under carry out calcination process, most afterwards through restore be made final catalyst.The activity stability of catalyst for preparing propylene with propane dehydrogenation, the selectivity of propylene and productivity of propylene prepared by this method is improved.
Description
Technical field
The present invention relates to a kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application.Relate in particular to one kind
Catalyst for preparing propylene with propane dehydrogenation suitable for fixed bed gas solid catalytic reaction and its preparation method and application, belongs to Industrial Catalysis
The catalyst of technical field and its preparation and application technology.
Background technology
Propane is a kind of important Organic Chemicals, is widely used in polypropylene, polyacrylonitrile, propylene oxide, acetone
Etc. chemical products.At present, propylene is mainly derived from naphtha steam cracking ethylene and the catalytic cracking process of petroleum refining.So
And in recent years, with the large-scale application of U.S.'s shale gas so that the raw material of cracking of ethylene factory is turned to by the naphtha of high price
Using cheap ethane, byproduct propylene amount is caused to be greatly decreased；The a large amount of propane of by-product, is urged by propane in U.S.'s shale gas
The method of fluidized dehydrogenation obtains, with the propylene compared with high added value, having important research significance with high selectivity.At present, in the world
Dehydrogenating propane technology is industrialized for the Oleflex techniques of UOP and the Catofin techniques of LUMMUS.Both at home and abroad it is built or
Above two technique is all from the dehydrogenating propane device built.
Uop Inc. uses platinum metal catalyst, and LUMMUS uses chromium metallic catalyst, the easy carbon distribution of catalyst and inactivation
Soon.UOP solves the problems, such as above-mentioned catalyst using Continuous Moving Bed, and LUMMUS then switches mutually solution using multiple parallel reactors
The certainly above problem, but plant investment is of high cost, and operating cost is high.
Realize that the key of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technology is to develop with high activity, high stability, highly selective
New catalyst.Currently, propane dehydrogenation catalyst is mainly that either molecular sieve supported chromium system or platinum group urges with aluminium oxide
Agent is main metal active constituent, and adds various auxiliary agents and attempt to improve the performance of catalyst.
CN1155451A discloses a kind of by group IVA metallic element, platinum group, alkali metal element, halogen family member
Element and element sulphur sequence are impregnated into aluminium oxide, silica, spinelle or the catalyst that molecular sieve is carrier, and in platinum family gold
Belong to needs to be handled with water vapour in element and IVA races metallic element.The catalyst reacts for C2~C5 dehydrating alkanes, has
Higher conversion ratio and selectivity.
CN101003458A discloses a kind of ordered structure carrier with parallel empty island and coating containing on this carrier
There is the coating of matrix, dehydrogenation active component, and the sectional area for applying thickness stomidium is not less than the 10% of carrier hole sectional area.Utilize this
Method, which carries out dehydrogenating propane reaction, can obtain higher conversion of propane and propene yield.
CN101380587A and CN101972664A, which is then individually disclosed, to be related to one kind and with skeleton contains rare earth elemental metals
Or the catalyst of the bimetallic molecular sieves of SnAl for carrier and preparation method thereof, respectively using platinum group as main catalytic
Agent, using IVA races metallic element, group ia or group iia metal as auxiliary agent, halogen is modifying agent, with high temperature resistant inorganic oxygen
Compound is the molding catalyst of binding agent.There is the catalyst preferable conversion of propane, propylene to select under high temperature, lower pressure
Selecting property and anti-carbon performance.
CN101884922A discloses a kind of use sol-gal process and tin component is introduced Aluminum sol, is used again after drying and moulding
Make Supported Pt Nanoparticles component and the catalyst of other metal promoters.The catalyst solves the tin component under the conditions of hot operation well
The problem of easily restoring and be precipitated, influencing catalytic performance.
Although in conclusion in the prior art using platinum group as the catalyst for preparing propylene with propane dehydrogenation of active component
The related research of system achieves larger progress, but there is no platinum group catalyst system easy in inactivation is fundamentally solved, turns
The technical issues of rate and relatively low selectivity.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof and should
With.The activity stability of catalyst for preparing propylene with propane dehydrogenation, the selectivity of propylene and productivity of propylene prepared by this method obtains
It improves.
One of the object of the invention is to provide a kind of catalyst for preparing propylene with propane dehydrogenation.The catalyst is using aluminium oxide as load
Body, using platinum group metal as active component, using carbon and tin as auxiliary agent；On the basis of catalyst quality, platinum element mass content
It is 0.001~5%, preferably 0.1~1%, further preferably 0.3~0.5%, tin metal element mass content is 0.001%
~5%, preferably 0.1~3%, further preferably 0.5~2.5%, carbon mass content are 0.001~1%, preferably
0.01~0.5%, further preferably 0.1~0.5%.
In above-mentioned catalyst, the platinum group metal is at least one kind in ruthenium, rhodium, palladium, osmium, iridium or platinum, preferably platinum
Belong to.
The two of the object of the invention are to provide a kind of preparation method of catalyst for preparing propylene with propane dehydrogenation, include the following steps：
(1) using aluminium oxide as carrier, using infusion process supporting platinum-group metals and tin；
(2) aluminium oxide of step (1) load active component and auxiliary agent is in H2And C2H4Mixed atmosphere under roasted,
Middle H2And C2H4Volume ratio be 1：1~1:30, calcination temperature is 300~500 DEG C, and roasting time is 3~15min；
(3) catalyst for preparing propylene with propane dehydrogenation is made in the material after step (2) roasting after carrying out reduction.
In the above method, using co-impregnation supporting platinum-group metals and tin, include dry and roasting process after dipping, preferably adopt
It is dried with rotary evaporation, calcination temperature is 450~650 DEG C.
The three of the object of the invention are to provide the application of more than one catalyst for preparing propylene with propane dehydrogenation, using propane as original
Material, preferably 400~650 DEG C of the temperature of reactor inlet, 540~620 DEG C；300~2000h of volume space velocity-1, preferably 500~
1500h-1；Reaction pressure not more than 0.05Mpa (gauge pressure).
Propane dehydrogenation catalyst prepared by the present invention, using platinum group metal as active component, using tin and carbon as auxiliary agent.It is described to urge
Agent conversion of propane, selectivity, anti-carbon performance are improved, therefore with preferable prospects for commercial application.
Specific embodiment
The present invention is further described in detail with reference to embodiment, but the present invention is not limited by these embodiments
System.Following % contents are mass content such as without special records.
Embodiment 1
Weigh 60g γ-Al2O3, 0.03mol/L H are impregnated at 75 DEG C2PtCl6With 0.2mol/L SnCl2In aqueous solution
Co-impregnation 0.5h, wherein liquor capacity are measured according to catalytic component mass content, and drying is obtained after 75 DEG C of rotary evaporations
Presoma is placed into Muffle furnace, and 3h is roasted in 450 DEG C of air.It takes out catalyst to be placed in tube furnace, in H2And C2H4Volume ratio
It is 1：15min, 500 DEG C of calcination temperature are roasted in 1 mixed atmosphere.Finally at 580 DEG C hydrogen reducing 1h obtain Pt-Sn-C
The mass content of propane dehydrogenation catalyst 1, wherein platinum is that 0.5%, Sn mass contents are 1.5%, and carbon mass content is 0.1%.
Embodiment 2
Weigh 60g γ-Al2O3, 0.03mol/L H are impregnated at 75 DEG C2PtCl6With 0.2mol/L SnCl2In aqueous solution
Co-impregnation 0.5h, wherein liquor capacity are measured according to catalytic component mass content, and drying is obtained after 75 DEG C of rotary evaporations
Presoma is placed into Muffle furnace, and 3h is roasted in 650 DEG C of air.It takes out catalyst to be placed in tube furnace, in H2And C2H4Volume ratio
It is 1：3min, 300 DEG C of calcination temperature are roasted in 30 mixed atmosphere.Finally at 580 DEG C hydrogen reducing 1h obtain Pt-Sn-C
It is 0.5% that propane dehydrogenation catalyst 2, the wherein mass content of the wherein platinum of catalyst 2, which are 0.3%, Sn contents, and carbon content is
0.5%.
Embodiment 3~6
Preparation method is same as Example 1, but catalyst activity component is different with the mass content of auxiliary agent, and catalyst is made
3~6.The mass percentage of 3 platinum of catalyst is that 0.2%, Sn contents are 0.6%, carbon content 0.025%.4 platinum of catalyst
Mass percentage is that 0.2%, Sn contents are 0.6%, carbon content 0.1%.The mass percentage of the wherein platinum of catalyst 5 is
0.1%, Sn content are 2.5%, carbon content 0.1%.The mass percentage of the wherein platinum of catalyst 6 is that 0.5%, Sn contents are
0.3%, carbon content 0.1%.
Catalyst prepared by the above method is completed for dehydrogenating propane experiment on fixed bed reactors.Wherein catalyst is filled out
Fill volume 30ml, 500~1500h of propane volume space velocity-1, reaction pressure is normal pressure, and reactor inlet temperature is 540~620 DEG C,
Dehydrogenating propane product is analyzed using HP7890 gas-chromatographies, and the experimental result that experimental period reaches 3 hours refers to table 1.
Table 1
As it can be seen from table 1 the single reaction time reaches 3 hours, catalyst still has preferable activity and selection
Property, there is preferable prospects for commercial application.
Claims (8)
1. a kind of catalyst for preparing propylene with propane dehydrogenation, it is characterised in that：The catalyst is using aluminium oxide as carrier, with platinum group metal
For active component, using carbon and tin as auxiliary agent；On the basis of catalyst quality, platinum group mass content is 0.3 ~ 0.5%,
Tin metal element mass content is 1.5 ~ 2.5%, and carbon mass content is 0.1 ~ 0.5%；Wherein, the platinum group metal and Xi Cai
It is loaded with infusion process.
2. catalyst according to claim 1, it is characterised in that：The platinum group metal is at least ruthenium, rhodium, palladium, osmium, iridium
Or one kind in platinum.
3. catalyst according to claim 2, it is characterised in that：The platinum group metal is platinum.
4. the preparation method of any catalyst of claims 1 to 3, it is characterised in that：Include the following steps：
（1）Using aluminium oxide as carrier, using infusion process supporting platinum-group metals and tin；
（2）Step（1）The aluminium oxide of load active component and auxiliary agent is in H2And C2H4Mixed atmosphere under roasted, wherein H2With
C2H4Volume ratio be 1：1~1:30, calcination temperature is 300 ~ 5000C, roasting time are 3 ~ 15 min；
（3）Step（2）Catalyst for preparing propylene with propane dehydrogenation is made in material after roasting after carrying out reduction.
5. according to the method described in claim 4, it is characterized in that：Using co-impregnation supporting platinum-group metals and tin, wrapped after dipping
Include dry and roasting process.
6. according to the method described in claim 5, it is characterized in that：It is dry to be dried using rotary evaporation, calcination temperature for 450 ~
6500C。
7. application of any catalyst of claims 1 to 3 in preparing propylene by dehydrogenating propane, it is characterised in that：Using propane as
Raw material, 400 ~ 650 DEG C of reactor inlet temperature, 300 ~ 2000 h of volume space velocity-1, reaction pressure not more than gauge pressure
0.05Mpa。
8. application according to claim 7, it is characterised in that：540 ~ 620 DEG C of reactor inlet temperature, volume space velocity 500 ~
1500 h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410461255.8A CN105396583B (en) | 2014-09-11 | 2014-09-11 | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410461255.8A CN105396583B (en) | 2014-09-11 | 2014-09-11 | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105396583A CN105396583A (en) | 2016-03-16 |
| CN105396583B true CN105396583B (en) | 2018-06-12 |
Family
ID=55462534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410461255.8A Active CN105396583B (en) | 2014-09-11 | 2014-09-11 | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105396583B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970931A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of catalyst of mixed alkanes dehydrogenation production alkene, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898131A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011109816B4 (en) * | 2011-08-09 | 2017-04-06 | Clariant Produkte (Deutschland) Gmbh | Catalyst material for the oxidation of hydrocarbons |
-
2014
- 2014-09-11 CN CN201410461255.8A patent/CN105396583B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898131A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 氧化铝改性及其负载Pt基催化剂;田利利;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130615(第6期);第B016-341页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105396583A (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105396582B (en) | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application | |
| CN105251486B (en) | Load type platinum series catalysts applied to preparing propylene by dehydrogenating propane and preparation method thereof | |
| CN111085199A (en) | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof | |
| CN105582979B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof | |
| CN104971717B (en) | The ZnO/Al of Pt modifications2O3Catalyst and its preparation method and application | |
| CN111408370B (en) | Supported PtZn intermetallic alloy catalyst and preparation method and application thereof | |
| CN106807405B (en) | A kind of preparation method and its catalyst of the catalyst for preparing propylene by dehydrogenating propane | |
| CN101623633A (en) | Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof | |
| CN106582629B (en) | A kind of catalyst of preparing propylene by dehydrogenating propane and its preparation method and application | |
| CN104588011B (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN103769079A (en) | Low carbon alkane dehydrogenation catalyst and its preparation method and application | |
| CN103349988A (en) | Platinoid bi-component catalyst as well as preparation method and application thereof | |
| CN102407169B (en) | Regeneration method of copper, ruthenium, cobalt, nickel, palladium and platinum-based metal catalysts | |
| CN103418377B (en) | The thin-shell catalyst of low-carbon alkene is prepared for dehydrogenating low-carbon alkane | |
| CN101898131A (en) | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof | |
| CN110237849A (en) | A kind of platinum based catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN106588544B (en) | Method for preparing propylene by propane dehydrogenation | |
| CN107537476A (en) | Dehydrogenation, preparation method and its usage | |
| CN111013642B (en) | Anti-carbon deposition catalyst for preparing propylene by propane dehydrogenation and preparation method thereof | |
| CN102989455A (en) | Low carbon alkane dehydrogenation olefin production catalyst and preparation method thereof | |
| CN105396583B (en) | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application | |
| CN107537587B (en) | Method for treating catalyst | |
| CN105689013A (en) | Regeneration method and application of low-alkane dehydrogenation catalyst | |
| CN108067228B (en) | Propane dehydrogenation catalyst and preparation method thereof | |
| CN102909012B (en) | Activation method for dehydrogenation catalyst |
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 |