CN104588011B - Alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a dehydrogenation catalyst. The method comprises the following steps: loading Sn by adopting an immersion process with alumina as a carrier; drying, roasting, and carrying out surface modification on the Sn supported alumina carrier by using an alcohol solvent; drying the modified Sn-containing alumina carrier, and loading an active component Pt by adopting the immersion process; and loading alkali metal Na. The catalyst prepared through the method can promote Pt-Sn interaction, so the selectivity of a target product propylene is improved, and the active stability of the catalyst is also improved.
Description
Technical field
The present invention relates to a kind of alkane dehydrogenating catalyst and preparation method thereof, relates in particular to a kind of dehydrogenating propane system third
Alkene catalyst and preparation method thereof.
Background technology
The exploitation of North America shale gas already leads to Gas Prices declining to a great extent relative to crude oil price, and in shale gas
Substantial amounts of condensed liquid（NGLs）Yield is also increased rapidly.Rich in low-carbon alkanes such as ethane, propane, butane in shale gas condensed liquid,
Ethane can produce ethene as cracking stock, therefore the demand of propylene rapid growth has only been unable to by FCC technologies.Will be natural
Gas（Conventional gas, shale gas, coal bed gas, combustible ice etc.）In dehydrogenating low-carbon alkane preparing low-carbon olefins be solve this ask
The effective way of topic.And with the increasingly scarcity of petroleum resources, the production of propylene is raw material to original from dependence oil merely
The diversified technology path transformation in material source, is increasingly becoming a kind of trend.In recent years, dehydrogenating propane produced the technology of propylene
The technology development for achieving large development, particularly dehydrogenating propane (PDH) propylene processed is very fast, has become the third-largest production of propylene
Method.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, carbon deposit with activity
The reason for metal sintering always affects catalyst activity and stability.Due to relatively low conversion of propane and harsh reaction bar
The shortening of catalyst life under part, makes PDH methods be restricted in commercial Application.Therefore, exploitation has high activity, Gao Xuan
The catalyst for preparing propylene with propane dehydrogenation of selecting property and high stability becomes the key of the technology.Patent CN1201715 disclose for
Low-carbon alkanes（C1~C5）The Pt-Sn-K/Al of dehydrogenation2O3The preparation method of catalyst.Patent CN101066532 discloses one kind and adopts
The method that Sn is incorporated into into ZSM-5 molecular sieve skeleton with Hydrothermal Synthesiss, and for propane dehydrogenation catalyst carrier, the catalysis for obtaining
Agent runs 100h, conversion of propane 30%, Propylene Selectivity more than 99%.CN1579616 patent reports are voluntarily researching and developing
Macropore, low heap ratio, the γ-Al with double-pore structure2O3Bead is carrier, for the catalyst of linear alkanes dehydrogenation, by urging
The modulation of agent, can improve the reactivity worth of dehydrogenating low-carbon alkane.USP4,914,075 discloses propane and other low-carbon alkanes
Dehydrogenation oxidation aluminium is the Pt base catalyst of carrier, with high alkane conversion and olefine selective.USP6,103,103 is disclosed
With borosilicate and alkali metal as carrier, platinum group metal active metal, zinc is the dehydrogenation of auxiliary agent to one kind, shows
Preferable dehydrogenation.
At present, the dehydrogenating propane research both at home and abroad with regard to aluminum oxide for the Pt-Sn class catalyst of carrier has a large amount of reports,
Focus mostly at aspects such as method for preparing catalyst, auxiliary agent and active metal allotments.How the interphase interaction of Pt-Sn is promoted, from
And the activity stability of the selectivity and catalyst for improving target product olefins is the focus of research.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof.Should
Catalyst prepared by method can promote the interphase interaction of Pt-Sn, improve selectivity and the catalyst of target product propylene
Activity stability.
A kind of preparation method of dehydrogenation, including following process：It is negative initially with infusion process with aluminum oxide as carrier
Carry Sn；Surface is carried out after drying and roasting to the alumina support for loading Sn using alcohols solvent to be modified；Modified aoxidizes containing Sn
Alumina supporter after drying, using infusion process load active component Pt；Final load Alkali-Metal Na.
The present invention relates to alumina support, can be existing product, it is also possible to as known to professional and technical personnel in the field
It is prepared by method.Above-mentioned alumina support can be spherical, bar shaped, microballoon or abnormity, and particle equivalent diameter is 0.1 ~ 5mm, excellent
Elect 0.5 ~ 2mm as.Carrying alumina surface area per unit volume is 200 ~ 240 m2/ g, pore volume is 0.60 ~ 0.80 cm3/g。
In dehydrogenation preparation method of the present invention, auxiliary agent Sn is incorporated in catalyst with dipping method.Sn predecessors can
Think cation pink salt, such as nitric acid tin, butter of tin, tin acetate, or stannic acid metalloid salt, such as sodium stannate, stannic acid
Potassium etc., preferably butter of tin.The content of Sn is calculated as the 0.1% ~ 10% of catalyst weight with simple substance, and preferably 1% ~ 5%.Auxiliary agent Sn
Dipping process can adopt method well known to those skilled in the art.Such as adopt following process：First using molten containing auxiliary agent Sn
Liquid impregnated carrier, dip time 1h ~ 72h, preferred 2h ~ 24h.It is dried after immersion tin, baking temperature is 60 DEG C ~ 150 DEG C, when being dried
Between be 1h ~ 24h, be dried 4h ~ 8h at preferably 80 DEG C ~ 120 DEG C.Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h,
Roasting 4h ~ 8h at preferably 500 DEG C ~ 700 DEG C.
The surface modifying method of stanniferous alumina support according to the present invention is to be heated to reflux carrying out table using alcohols solvent
Face is processed.In surface modifying method according to the present invention, the alcohols is the one kind or several in methyl alcohol, ethanol, propyl alcohol, isopropanol
Plant, preferably methyl alcohol, ethanol or the two mixed solvent.Process of Surface Modification is as follows：The heating of Sn alumina supports will be contained to vacuumize
Process, treatment temperature is 60 DEG C ~ 100 DEG C, and preferably 70 DEG C ~ 90 DEG C, pressure is less than 30kPa in vacuum system, preferably less than
20 kPa, process time is 0.5h ~ 8h, preferably 1h ~ 4h；After cooling, under vacuum conditions, alcohols solvent is added, recover normal
Pressure, is heated to reflux, and less than 5 DEG C ~ 10 DEG C of solvent or mixed solvent boiling point, return time is 2h ~ 12h to reflux temperature, and preferably 4h ~
8h；Backflow terminate after, separation of solid and liquid is dried solid after separation, baking temperature be 60 DEG C ~ 150 DEG C, drying time for 1h ~
24h, at preferably 80 DEG C ~ 120 DEG C 4h ~ 8h is dried.
In alkane dehydrogenating catalyst preparation method of the present invention, the introducing method of active component Pt is adopted and is not added with competitive adsorbate
The dipping method of hydrochloric acid.The predecessor of Pt can be chloroplatinic acid, the organic complex salt alternatively containing Pt, preferably chloroplatinic acid.Leaching
Stain liquid can be the aqueous solution, or the organic solution containing Pt.Active component Pt with simple substance be calculated as catalyst weight 0.1% ~
2%, preferably 0.2% ~ 0.8%.Following process can be adopted：First using the modified alumina support containing Sn of the solution impregnation containing Pt, leaching
Stain time 1h ~ 72h, preferred 2h ~ 24h.It is dried after dipping, baking temperature is 60 DEG C ~ 150 DEG C, drying time is 1h ~ 24h, preferably
To be dried 4h ~ 8h at 80 DEG C ~ 120 DEG C.Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h, preferably 600 DEG C ~ 800
Roasting 4h ~ 8h at DEG C.
In the preparation method of alkane dehydrogenating catalyst of the present invention, the solid after load active component Pt need not enter water-filling steaming
The process of qi exhaustion chlorine.The direct carrying alkali metal Na of solid.The carrying method of Alkali-Metal Na is dipping well known to those skilled in the art
Method.The predecessor of Na is soluble salt containing Na, can be inorganic salts, or organic salt, preferably sodium nitrate.Auxiliary agent
Na is calculated as the 0.1% ~ 3% of catalyst weight with simple substance, and preferably 0.5% ~ 2%.Following process can be adopted：First using molten containing Na
Liquid steep solids, dip time 1h ~ 16h, preferred 2h ~ 8h.It is dried after dipping, baking temperature is 60 DEG C ~ 150 DEG C, drying time
For 1h ~ 24h, at preferably 80 DEG C ~ 120 DEG C 4h ~ 8h is dried.Sintering temperature is 500 DEG C ~ 900 DEG C, and roasting time 2h ~ 24h is excellent
Roasting 4h ~ 8h at electing 600 DEG C ~ 800 DEG C as.
Catalyst for dehydrogenation of low-carbon paraffin prepared by a kind of employing said method, with aluminum oxide as carrier, with Pt as activearm
Point, Sn is the second auxiliary agent as the first auxiliary agent, Alkali-Metal Na, and the content of Sn is calculated as the 0.1% ~ 10% of catalyst weight with simple substance,
Preferably 1% ~ 5%, active component Pt is calculated as the 0.1% ~ 2% of catalyst weight with simple substance, and preferably 0.2% ~ 0.8%, Na is with simple substance
It is calculated as the 0.1% ~ 3% of catalyst weight, preferably 0.5% ~ 2%.
In the present invention, carry out surface to the alumina support for loading Sn using alcohols solvent to be modified, alcohol solvent molecules
The adsorption potential of alumina carrier surface containing Sn can be preferentially occupied, what active metal Pt can be oriented anchors to exposed Sn surfaces,
Make Pt-Sn preferably form matching, produce synergy, improve the selectivity of propylene and the activity stability of catalyst.Together
When surface treatment of the alcohols solvent to alumina support, dechlorination process can be saved, it is to avoid the agglomeration of Pt particles, improve
Catalyst activity.Additionally, alcohols solvent is processed the surface reflow of alumina support, alumina carrier surface property is improved,
Reduce catalyst surface acid, suppress carbon distribution, improve catalyst stability.Method for preparing catalyst of the present invention is simple, technique skill
Art is ripe, is conducive to the industrial production of catalyst.
Specific embodiment
The technology of the present invention is described further below by the enforcement of dehydrogenating propane.
Example 1
Weigh commercial alumina carrier（It is spherical, diameter 0.5mm, pore volume 0.71cm3/g, specific surface area 224m2/ g, below
Embodiment uses the carrier）30g, is added dropwise deionized water to just profit, and the volume for consuming water is 27mL.Account for by Sn contents and finally urge
Agent 3wt% is counted, and is weighed the butter of tin containing 0.9gSn and is dissolved in deionized water, is settled to 27mL.It is molten containing Sn by having configured
Liquid is added into 30g alumina supports, is well mixed, aging 2h.80 DEG C of dryings 8 hours, then in 600 DEG C of roastings 4 hours.Roasting
Sample is placed in Rotary Evaporators and vacuumizes process after burning, temperature 70 C, vacuum degree control in below 10kPa, after processing 1 hour
Cooling, adds 100mL methyl alcohol, replys normal pressure, is heated to reflux, 55 DEG C of heating-up temperature, process time 4 hours.After backflow terminates, Gu
Liquid is separated.Solid is dried after separating, and baking temperature is 80 DEG C, time 4h.Impregnate into above-mentioned modified carrier silica gel, always
Change 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 500 DEG C.Account for based on catalyst 0.6wt% by Pt contents, weigh containing Pt
The chloroplatinic acid of 0.18g is dissolved in deionized water, is settled to 27mL, is added into above-mentioned sample, aging 3 hours, 80 DEG C of dryings 8
Hour, roasting 4 hours in 600 DEG C.The appropriate sodium nitrate configuration aqueous solution is weighed, at 70 DEG C 2h is impregnated, it is same after Pt with soaking
Condition is dried, roasting.The content of each component is in prepared catalyst：The wt% of Pt 0.6wt%, Sn3wt%, Na 1.0.Gained catalysis
Agent is designated as C-1.
Appreciation condition：Catalyst quality 3.0g, hydrogen atmosphere reduction, the mass space velocity of propane is 3h-1, reaction pressure
0.1MPa, reaction temperature is 630 DEG C.Following examples gained evaluating catalyst condition is same.
Example 2
Process prepares Jing Ethanol Treatment catalyst, each component in 70 DEG C of prepared catalyst of reflux temperature as described in embodiment 1
Content be：The wt% of Pt 0.6wt%, Sn3.0wt%, Na 1.0.Gained catalyst is designated as C-2.
Example 3
Process prepares Jing methyl alcohol, alcohol mixed solvent and processes catalyst as described in embodiment 1, and methyl alcohol, ethanol mol ratio are
1:3,66 DEG C of reflux temperature, the content of each component is in prepared catalyst：The wt% of Pt 0.6wt%, Sn3.0wt%, Na 1.0.Institute
Obtain catalyst and be designated as C-3.
Example 4
Process prepares Jing methyl alcohol, alcohol mixed solvent and processes catalyst as described in embodiment 1, and methyl alcohol, ethanol mol ratio are
1:1,62 DEG C of reflux temperature, the content of each component is in prepared catalyst：The wt% of Pt 0.6wt%, Sn3.0wt%, Na 1.0.Institute
Obtain catalyst and be designated as C-4.
Example 5
Process prepares Jing methyl alcohol, alcohol mixed solvent and processes catalyst as described in embodiment 1, and methyl alcohol, ethanol mol ratio are
3:1,58 DEG C of reflux temperature, the content of each component is in prepared catalyst：The wt% of Pt 0.6wt%, Sn3.0wt%, Na 1.0.Institute
Obtain catalyst and be designated as C-5.
Example 6
Process prepares Jing Ethanol Treatment catalyst, each component in 70 DEG C of prepared catalyst of reflux temperature as described in embodiment 2
Content be：The wt% of Pt 0.3wt%, Sn2.0wt%, Na 2.0.Gained catalyst is designated as C-6.
Example 7
Process prepares Jing Ethanol Treatment catalyst, each component in 70 DEG C of prepared catalyst of reflux temperature as described in embodiment 2
Content be：Pt 0.7wt%, Sn1.0wt%, Na 0.5wt%.Gained catalyst is designated as C-7.
Example 8
Process prepares Jing Ethanol Treatment catalyst, each component in 70 DEG C of prepared catalyst of reflux temperature as described in embodiment 2
Content be：Pt 0.5wt%, Sn2.0wt%, Na 1.0wt%.Gained catalyst is designated as C-8.
Comparative example
The process as described in embodiment 2 prepares catalyst without reflow treatment, and the content that each component in catalyst is obtained is：Pt
The wt% of 0.6wt%, Sn3.0wt%, Na 1.0.Gained catalyst is designated as D-1.
The reactivity worth of the catalyst of table 1
| Catalyst | Conversion of propane, % | Propylene Selectivity, % |
| C-1 | 31.4 | 98.3 |
| C-2 | 32.2 | 98.6 |
| C-3 | 32.5 | 98.1 |
| C-4 | 32.8 | 98.4 |
| C-5 | 31.9 | 98.9 |
| C-6 | 28.1 | 98.7 |
| C-7 | 33.8 | 99.1 |
| C-8 | 32.0 | 98.9 |
| D-1 | 27.4 | 92.3 |
Claims (13)
1. a kind of preparation method of dehydrogenation, it is characterised in that：Including following process：With aluminum oxide as carrier, adopt first
Sn is loaded with infusion process；Surface is carried out after drying and roasting to the alumina support for loading Sn using alcohols solvent to be modified；It is modified
Alumina support containing Sn after drying, using infusion process load active component Pt；Final load Alkali-Metal Na；
The surface modifying method of stanniferous alumina support is to be heated to reflux carrying out surface using alcohols solvent to be modified；
The Process of Surface Modification is as follows：
（1）The heating of Sn alumina supports will be contained and vacuumize process, treatment temperature will be 60 DEG C ~ 100 DEG C, and pressure is less than in vacuum system
30kPa, process time is 0.5h ~ 8h；
（2）After cooling, under vacuum conditions, add alcohols solvent, recover normal pressure, be heated to reflux, reflux temperature less than solvent or
5 DEG C ~ 10 DEG C of mixed solvent boiling point, return time is 2h ~ 12h；
（3）After backflow terminates, separation of solid and liquid is dried solid after separation, and baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h
~24h。
2. method according to claim 1, it is characterised in that：Alumina support be spherical or bar shaped, particle equivalent diameter
For 0.1 ~ 5mm, specific surface is 200 ~ 240 m2/ g, pore volume is 0.60 ~ 0.80 cm3/g。
3. method according to claim 1, it is characterised in that：Auxiliary agent Sn is incorporated in catalyst with dipping method, before Sn
It is cation pink salt or stannic acid metalloid salt to drive thing.
4. method according to claim 3, it is characterised in that：Cation pink salt is selected from nitric acid tin, butter of tin or acetic acid
Tin, stannic acid metalloid salt is selected from sodium stannate or potassium stannate.
5. method according to claim 1, it is characterised in that：The dipping process of auxiliary agent Sn is as follows：First adopt Sn containing auxiliary agent
Solution impregnating carrier, dip time 1h ~ 72h；After immersion tin be dried, baking temperature be 60 DEG C ~ 150 DEG C, drying time be 1h ~
24h；Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h.
6. method according to claim 1, it is characterised in that：The alcohols is in methyl alcohol, ethanol, propyl alcohol, isopropanol
One or more.
7. method according to claim 1, it is characterised in that：The introducing method of active component Pt is adopted and is not added with competitive Adsorption
The dipping method of agent hydrochloric acid.
8. method according to claim 1, it is characterised in that：The predecessor of Pt is chloroplatinic acid or the organic complex containing Pt
Salt, maceration extract is the platiniferous aqueous solution or is the organic solution containing Pt.
9. method according to claim 1, it is characterised in that：Active component Pt dipping adopts following process：First adopt and contain
The modified alumina support containing Sn of the solution impregnation of Pt, dip time 1h ~ 72h；It is dried after dipping, baking temperature is 60 DEG C ~ 150
DEG C, drying time is 1h ~ 24h；Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h.
10. method according to claim 1, it is characterised in that：Solid after load active component Pt need not enter water-filling
Steam dechlorination is processed, the direct carrying alkali metal Na of solid.
11. methods according to claim 1, it is characterised in that：The predecessor of Alkali-Metal Na is soluble salt containing Na, adopts
Impregnated with following process：First using the solution impregnation solid containing Na, dip time 1h ~ 16h；It is dried after dipping, baking temperature is
60 DEG C ~ 150 DEG C, drying time is 1h ~ 24h；Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h.
A kind of 12. dehydrogenations of employing claim 1-11 either method, it is characterised in that：With aluminum oxide as carrier, with
Pt is active component, and Sn is the second auxiliary agent as the first auxiliary agent, Alkali-Metal Na, and the content of Sn is calculated as catalyst weight with simple substance
0.1% ~ 10%, active component Pt is calculated as catalyst weight with 0.1% ~ 2%, the Na that simple substance is calculated as catalyst weight with simple substance
0.1%~3%。
13. catalyst according to claim 12, it is characterised in that：The content of Sn is calculated as catalyst weight with simple substance
1% ~ 5%, active component Pt with simple substance be calculated as 0.2% ~ 0.8%, Na of catalyst weight with simple substance be calculated as catalyst weight 0.5% ~
2%。
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| CN106732574B (en) * | 2016-11-14 | 2019-10-11 | 中国海洋石油集团有限公司 | A kind of alkane dehydrogenating catalyst and preparation method thereof of the Pt crystal containing mixing |
| CN106693993B (en) * | 2016-12-21 | 2019-04-30 | 北京赛诺时飞石化科技有限公司 | A kind of sulfur-type catalyst for dehydrogenation of low-carbon paraffin and preparation method |
| CN109126788B (en) * | 2018-08-01 | 2021-03-05 | 西安凯立新材料股份有限公司 | Platinum-alumina composite catalyst for alkane dehydrogenation |
| CN111992208B (en) * | 2020-09-01 | 2023-03-07 | 辽宁石油化工大学 | Preparation method of organic alcohol treated propane dehydrogenation catalyst |
| CN112007638B (en) * | 2020-09-01 | 2023-04-07 | 辽宁石油化工大学 | Preparation method of propane dehydrogenation catalyst prepared by controlling Pt grain size |
| CN111992207B (en) * | 2020-09-01 | 2023-04-07 | 辽宁石油化工大学 | Preparation method of Pt-based propane dehydrogenation catalyst |
| CN112023921B (en) * | 2020-09-01 | 2023-07-18 | 辽宁石油化工大学 | Preparation method of Pt-based catalyst with high dispersion of active component |
| CN112007639B (en) * | 2020-09-01 | 2023-03-21 | 辽宁石油化工大学 | Preparation method of dehydrogenation catalyst with low carbon deposition rate |
| CN115518651B (en) * | 2021-06-24 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by alkane dehydrogenation and preparation method and application thereof |
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Effective date of registration: 20230901 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |