CN104588011A - 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, relate in particular to a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof.
Background technology
The exploitation of North America shale gas has caused Gas Prices declining to a great extent relative to crude oil price, and condensed liquids a large amount of in shale gas (NGLs) output also increases rapidly.Be rich in the low-carbon alkanes such as ethane, propane, butane in shale gas condensed liquid, ethane can produce ethene as cracking stock, therefore only can not the demand that increases fast of propylene by FCC technology.The effective way addressed this problem by the dehydrogenating low-carbon alkane preparing low-carbon olefins in natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.).And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, also becomes a kind of trend gradually.In recent years, the technology that dehydrogenating propane produces propylene achieved large development, and particularly the technical development of dehydrogenating propane (PDH) propylene processed is very fast, has become the third-largest propylene production.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, limits by thermodynamical equilibrium, severe reaction conditions, and it is the reason affecting catalyst activity and stability that carbon deposit and active metal sinter always.Due to the shortening of catalyst life under lower conversion of propane and harsh reaction condition, PDH method is restricted when commercial Application.Therefore, the key that the catalyst for preparing propylene with propane dehydrogenation with high activity, high selectivity and high stability becomes this technology is developed.Patent CN1201715 discloses the Pt-Sn-K/Al for low-carbon alkanes (C1 ~ C5) dehydrogenation
2o
3the preparation method of catalyst.Patent CN101066532 discloses a kind of method adopting Hydrothermal Synthesis Sn to be incorporated into ZSM-5 molecular sieve skeleton, and for propane dehydrogenation catalyst carrier, the catalyst obtained runs 100h, conversion of propane 30%, Propylene Selectivity more than 99%.CN1579616 patent reports the macropore researched and developed voluntarily, low heap ratio, has the γ-Al of double-pore structure
2o
3bead is carrier, for the catalyst of linear alkanes dehydrogenation, by the modulation of catalyst, can improve the reactivity worth of dehydrogenating low-carbon alkane.USP4,914,075 to disclose propane and other dehydrogenating low-carbon alkane aluminium oxide be that the Pt of carrier is catalyst based, has high alkane conversion and olefine selective.USP6,103,103 disclose a kind of with borosilicate and alkali metal for carrier, platinum group metal active metal, zinc is the dehydrogenation of auxiliary agent, shows good dehydrogenation.
At present, be the existing a large amount of report of dehydrogenating propane research of the Pt-Sn class catalyst of carrier both at home and abroad about aluminium oxide, focus mostly in method for preparing catalyst, auxiliary agent and active metal allotment etc.How to promote the interphase interaction of Pt-Sn, thus the activity stability improving the selective and catalyst of target product olefins is the focus of research.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof.Catalyst prepared by the method can promote the interphase interaction of Pt-Sn, improves the activity stability of the selective and catalyst of target product propylene.
A preparation method for dehydrogenation, comprises following process: take aluminium oxide as carrier, first adopts infusion process load Sn; Alcohols solvent is used to carry out surface modification to the alumina support of load Sn after drying and roasting; Modified contains Sn alumina support after drying, adopts infusion process load active component Pt; Final load Alkali-Metal Na.
The present invention relates to alumina support, can be existing product, prepared by the method also can known by professional and technical personnel in the field.Above-mentioned alumina support can be spherical, bar shaped, microballoon or abnormity, and particle equivalent diameter is 0.1 ~ 5mm, is preferably 0.5 ~ 2mm.Carrying alumina surface area per unit volume is 200 ~ 240 m
2/ g, pore volume is 0.60 ~ 0.80 cm
3/ g.
In dehydrogenation preparation method of the present invention, auxiliary agent Sn is incorporated in catalyst with dipping method.Sn predecessor can be cationic tin salt, as nitric acid tin, butter of tin, tin acetate etc., also can be stannic acid metalloid salt, as sodium stannate, potassium stannate etc., is preferably butter of tin.The content of Sn counts 0.1% ~ 10% of catalyst weight with simple substance, is preferably 1% ~ 5%.The dipping process of auxiliary agent Sn can adopt method well known to those skilled in the art.As adopted following process: first adopt the solution impregnating carrier containing auxiliary agent Sn, dip time 1h ~ 72h, preferred 2h ~ 24h.Dry after immersion tin, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C.Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 500 DEG C ~ 700 DEG C.
The surface modifying method of the stanniferous alumina support that the present invention relates to carries out surface treatment for adopting alcohols solvent to add hot reflux.In the surface modifying method that the present invention relates to, described alcohols is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, is preferably methyl alcohol, ethanol or the two mixed solvent.Process of Surface Modification is as follows: will vacuumize process containing the heating of Sn alumina support, treatment temperature is 60 DEG C ~ 100 DEG C, and be preferably 70 DEG C ~ 90 DEG C, in vacuum system, pressure is lower than 30kPa, and be preferably lower than 20 kPa, the processing time is 0.5h ~ 8h, is preferably 1h ~ 4h; After cooling, under vacuum conditions, add alcohols solvent, recover normal pressure, add hot reflux, reflux temperature is lower than solvent or mixed solvent boiling point 5 DEG C ~ 10 DEG C, and return time is 2h ~ 12h, is preferably 4h ~ 8h; After backflow terminates, Separation of Solid and Liquid, solid drying after being separated, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C.
In alkane dehydrogenating catalyst preparation method of the present invention, the introducing method of active component Pt adopts the dipping method not adding competitive adsorbate hydrochloric acid.The predecessor of Pt can be chloroplatinic acid, also can be the organic complex salt containing Pt, is preferably chloroplatinic acid.Maceration extract can be the aqueous solution, also can for the organic solution containing Pt.Active component Pt counts 0.1% ~ 2% of catalyst weight with simple substance, is preferably 0.2% ~ 0.8%.Following process can be adopted: first adopt the solution impregnation modification containing Pt to contain Sn alumina support, dip time 1h ~ 72h, preferred 2h ~ 24h.Dry after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C.Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 600 DEG C ~ 800 DEG C.
In the preparation method of alkane dehydrogenating catalyst of the present invention, the solid after load active component Pt does not need to carry out steam dechlorination process.The direct carrying alkali metal Na of solid.The carrying method of Alkali-Metal Na is dipping method well known to those skilled in the art.The predecessor of Na is that solubility contains Na salt, and can be inorganic salts, also can be organic salt, is preferably sodium nitrate.Auxiliary agent Na counts 0.1% ~ 3% of catalyst weight with simple substance, is preferably 0.5% ~ 2%.Following process can be adopted: first adopt the solution impregnation solid containing Na, dip time 1h ~ 16h, preferred 2h ~ 8h.Dry after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C.Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 600 DEG C ~ 800 DEG C.
A kind of catalyst for dehydrogenation of low-carbon paraffin adopting said method to prepare, take aluminium oxide as carrier, take Pt as active component, Sn is as the first auxiliary agent, and Alkali-Metal Na is the second auxiliary agent, the content of Sn counts 0.1% ~ 10% of catalyst weight with simple substance, be preferably 1% ~ 5%, active component Pt and count 0.1% ~ 2% of catalyst weight with simple substance, be preferably 0.2% ~ 0.8%, Na counts 0.1% ~ 3% of catalyst weight with simple substance, is preferably 0.5% ~ 2%.
In the present invention, alcohols solvent is used to carry out surface modification to the alumina support of load Sn, alcohol solvent molecules can preferentially occupy containing Sn alumina carrier surface adsorption potential, active metal Pt can be directed anchor to exposed Sn surface, Pt-Sn is made better to form coupling, produce synergy, improve the activity stability of the selective of propylene and catalyst.Alcohols solvent is to the surface treatment of alumina support simultaneously, can save dechlorination process, avoid the agglomeration of Pt particle, improves catalyst activity.In addition, alcohols solvent, to the surface reflow process of alumina support, improves alumina carrier surface character, reduces catalyst surface acid, suppresses carbon distribution, improves catalyst stability.Method for preparing catalyst of the present invention is simple, and mature technology, is conducive to the industrial production of catalyst.
Detailed description of the invention
Enforcement below by dehydrogenating propane is described further technology of the present invention.
Example 1
Take commercial alumina carrier (spherical, diameter 0.5mm, pore volume 0.71cm3/g, specific area 224m
2/ g, following examples all use this carrier) 30g, drip deionized water to just moistening, the volume consuming water is 27mL.Account for final catalyst 3wt% by Sn content, the butter of tin taken containing 0.9gSn is dissolved in deionized water, is settled to 27mL.By being added in 30g alumina support containing Sn solution of configuring, mix, aging 2h.80 DEG C of dryings 8 hours, then 600 DEG C of roastings 4 hours.After roasting, sample is placed in Rotary Evaporators and vacuumizes process, temperature 70 C, and vacuum degree control, at below 10kPa, processes after 1 hour and lowers the temperature, add 100mL methyl alcohol, reply normal pressure, add hot reflux, heating-up temperature 55 DEG C, 4 hours processing times.After backflow terminates, Separation of Solid and Liquid.Solid drying after being separated, baking temperature is 80 DEG C, time 4h.To flooding in above-mentioned modified carrier silica gel, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 500 DEG C.Account for catalyst 0.6wt% by Pt content, the chloroplatinic acid taken containing Pt 0.18g is dissolved in deionized water, is settled to 27mL, is added in above-mentioned sample, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 600 DEG C.Take the appropriate sodium nitrate configuration aqueous solution, at 70 DEG C, flood 2h, roasting dry with similarity condition after leaching Pt.In obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3wt%, Na 1.0 wt%.Gained catalyst is designated as C-1.
Appreciation condition: catalyst quality 3.0g, hydrogen atmosphere reduces, and 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
By described in embodiment 1, process preparation is through Ethanol Treatment catalyst, and in reflux temperature 70 DEG C of obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3.0wt%, Na 1.0 wt%.Gained catalyst is designated as C-2.
Example 3
By described in embodiment 1, process preparation is through methyl alcohol, alcohol mixed solvent process catalyst, and methyl alcohol, ethanol mol ratio are 1:3, reflux temperature 66 DEG C, and in obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3.0wt%, Na 1.0 wt%.Gained catalyst is designated as C-3.
Example 4
By described in embodiment 1, process preparation is through methyl alcohol, alcohol mixed solvent process catalyst, and methyl alcohol, ethanol mol ratio are 1:1, reflux temperature 62 DEG C, and in obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3.0wt%, Na 1.0 wt%.Gained catalyst is designated as C-4.
Example 5
By described in embodiment 1, process preparation is through methyl alcohol, alcohol mixed solvent process catalyst, and methyl alcohol, ethanol mol ratio are 3:1, reflux temperature 58 DEG C, and in obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3.0wt%, Na 1.0 wt%.Gained catalyst is designated as C-5.
Example 6
By described in embodiment 2, process preparation is through Ethanol Treatment catalyst, and in reflux temperature 70 DEG C of obtained catalyst, the content of each component is: Pt 0.3wt%, Sn2.0wt%, Na 2.0 wt%.Gained catalyst is designated as C-6.
Example 7
By described in embodiment 2, process preparation is through Ethanol Treatment catalyst, and in reflux temperature 70 DEG C of obtained catalyst, the content of each component is: Pt 0.7wt%, Sn1.0wt%, Na 0.5wt%.Gained catalyst is designated as C-7.
Example 8
By described in embodiment 2, process preparation is through Ethanol Treatment catalyst, and in reflux temperature 70 DEG C of obtained catalyst, the content of each component is: Pt 0.5wt%, Sn2.0wt%, Na 1.0wt%.Gained catalyst is designated as C-8.
Comparative example
By process described in embodiment 2 without reflow treatment Kaolinite Preparation of Catalyst, in obtained catalyst, the content of each component is: Pt 0.6wt%, Sn3.0wt%, Na 1.0 wt%.Gained catalyst is designated as D-1.
The reactivity worth of table 1 catalyst
| 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 (15)
1. a preparation method for dehydrogenation, is characterized in that: comprise following process: take aluminium oxide as carrier, first adopts infusion process load Sn; Alcohols solvent is used to carry out surface modification to the alumina support of load Sn after drying and roasting; Modified contains Sn alumina support after drying, adopts infusion process load active component Pt; Final load Alkali-Metal Na.
2. method according to claim 1, is characterized in that: alumina support is spherical, bar shaped, microballoon or abnormity, and particle equivalent diameter is 0.1 ~ 5mm, and specific surface is 200 ~ 240 m
2/ g, pore volume is 0.60 ~ 0.80 cm
3/ g.
3. method according to claim 1, is characterized in that: auxiliary agent Sn is incorporated in catalyst with dipping method, and Sn predecessor is cation pink salt or stannic acid metalloid salt.
4. method according to claim 3, is characterized in that: cation pink salt comprises nitric acid tin, butter of tin, tin acetate, and stannic acid metalloid salt comprises sodium stannate, potassium stannate.
5. method according to claim 1, is characterized in that: the dipping process of auxiliary agent Sn is as follows: first adopt the solution impregnating carrier containing auxiliary agent Sn, dip time 1h ~ 72h, preferred 2h ~ 24h; Dry after immersion tin, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C; Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 500 DEG C ~ 700 DEG C.
6. method according to claim 1, is characterized in that: the surface modifying method of stanniferous alumina support carries out surface treatment for adopting alcohols solvent to add hot reflux.
7. the method according to claim 1 or 6, is characterized in that: described alcohols is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, is preferably methyl alcohol, ethanol or the two mixed solvent.
8. method according to claim 1, is characterized in that: Process of Surface Modification is as follows:
(1) will vacuumize process containing the heating of Sn alumina support, treatment temperature is 60 DEG C ~ 100 DEG C, and be preferably 70 DEG C ~ 90 DEG C, in vacuum system, pressure is lower than 30kPa, and be preferably lower than 20 kPa, the processing time is 0.5h ~ 8h, is preferably 1h ~ 4h;
(2) after cooling, under vacuum conditions, add alcohols solvent, recover normal pressure, add hot reflux, reflux temperature is lower than solvent or mixed solvent boiling point 5 DEG C ~ 10 DEG C, and return time is 2h ~ 12h, is preferably 4h ~ 8h;
(3), after backflow terminates, Separation of Solid and Liquid, solid drying after being separated, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C.
9. method according to claim 1, is characterized in that: the introducing method of active component Pt adopts the dipping method not adding competitive adsorbate hydrochloric acid.
10. method according to claim 1, is characterized in that: the predecessor of Pt is chloroplatinic acid or the organic complex salt containing Pt, and maceration extract is the aqueous solution or is the organic solution containing Pt.
11. methods according to claim 1, is characterized in that: active component Pt dipping adopts following process: first adopt the solution impregnation modification containing Pt to contain Sn alumina support, dip time 1h ~ 72h, preferred 2h ~ 24h; Dry after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C; Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 600 DEG C ~ 800 DEG C.
12. methods according to claim 1, is characterized in that: the solid after load active component Pt does not need to carry out steam dechlorination process, the direct carrying alkali metal Na of solid.
13. methods according to claim 1 or 12, is characterized in that: the predecessor of Alkali-Metal Na is that solubility contains Na salt, adopt following process to flood: first to adopt the solution impregnation solid containing Na, dip time 1h ~ 16h, preferred 2h ~ 8h; Dry after dipping, baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4h ~ 8h at being preferably 80 DEG C ~ 120 DEG C; Sintering temperature is 500 DEG C ~ 900 DEG C, roasting time 2h ~ 24h, roasting 4h ~ 8h at being preferably 600 DEG C ~ 800 DEG C.
14. 1 kinds adopt the catalyst for dehydrogenation of low-carbon paraffin described in claim 1-13 either method, it is characterized in that: take aluminium oxide as carrier, take Pt as active component, Sn is as the first auxiliary agent, Alkali-Metal Na is the second auxiliary agent, the content of Sn is counted 0.1% ~ 10%, active component Pt of catalyst weight and is counted 0.1% ~ 2%, Na of catalyst weight with simple substance and count 0.1% ~ 3% of catalyst weight with simple substance with simple substance.
15. catalyst according to claim 14, is characterized in that: the content of Sn is counted 1% ~ 5%, active component Pt of catalyst weight and counted 0.2% ~ 0.8%, Na of catalyst weight with simple substance and count 0.5% ~ 2% of catalyst weight with simple substance with simple substance.
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| CN106693993A (en) * | 2016-12-21 | 2017-05-24 | 北京赛诺时飞石化科技有限公司 | Sulfur-containing light alkane dehydrogenation catalyst and preparation method thereof |
| CN106732574A (en) * | 2016-11-14 | 2017-05-31 | 中国海洋石油总公司 | A kind of alkane dehydrogenating catalyst containing mixing Pt crystal and preparation method thereof |
| CN109126788A (en) * | 2018-08-01 | 2019-01-04 | 西安凯立新材料股份有限公司 | A kind of platinum oxidation aluminium composite catalyst of dehydrating alkanes |
| CN111992207A (en) * | 2020-09-01 | 2020-11-27 | 辽宁石油化工大学 | Preparation method of Pt-based propane dehydrogenation catalyst |
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