CN103406142A - Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst - Google Patents
Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst Download PDFInfo
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- CN103406142A CN103406142A CN2013103022116A CN201310302211A CN103406142A CN 103406142 A CN103406142 A CN 103406142A CN 2013103022116 A CN2013103022116 A CN 2013103022116A CN 201310302211 A CN201310302211 A CN 201310302211A CN 103406142 A CN103406142 A CN 103406142A
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Abstract
The invention relates to a preparation method of a P2O5 modified micro-porous molecular sieve shape-selective catalyst. The method adopts micro-porous molecular sieve ZSM-5 or MCM-22 as a matrix and phosphate as a precursor, P2O5 is loaded on the external surface of the micro-porous molecular sieve through a dipping and programmed heating roasting process, and the content of P2O5 in the shape-selective catalyst is 1-15% of the total mass of the catalyst. The shape-selective catalyst obtained in the invention has a very good shape-selective catalysis effect on a toluene disproportionation process, and the preparation method of the catalyst is simple.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, particularly a kind of P for the synthetic paraxylene process of toluene disproportionation
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst.
Background technology
The process of the synthetic paraxylene of toluene disproportionation is typical shape selective catalysis process.Micro porous molecular sieve such as ZSM-5 and MCM-22 are toluene disproportionation process shape-selective catalysts commonly used.Yet, because these micro porous molecular sieve outer surfaces have a large amount of acidic sites, this just causes the paraxylene generated in molecular sieve pore passage in the toluene disproportionation process to be easy to, on the acidic site of molecular sieve outer surface, isomerization reaction occurs, thereby has reduced the selective of contraposition product.Obtaining paraxylene and just must carry out modification to reduce the quantity of its outer surface acidity position to micro porous molecular sieve for high selectivity.Common method of modifying has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre-carbon distribution and metal oxide modified.Although the method for siliceous deposits can effectively improve the Shape-selective of molecular sieve catalyst, but because the active force between molecular sieve surface hydroxyl and deposit is very weak, often need the deposition of 3～4 times just can reach effect preferably, therefore operation is more loaded down with trivial details, and energy consumption is higher.Pre-carbon distribution also can improve the Shape-selective of molecular sieve catalyst, but because the catalyst after regeneration also must carry out again pre-carbon distribution, therefore operates loaded down with trivial detailsly, and also only limits at present laboratory research.
Adopt oxide modifying to cover the operation of molecular sieve outer surface acidity position very simple, and once just can complete covering preferably.Conventional P
2O
5Modified micropore molecular sieve shape-selective catalyst often adopts phosphoric acid as P
2O
5Predecessor, and phosphoric acid not only is scattered in the micro porous molecular sieve outer surface in dipping process, also can be scattered in the duct of micro porous molecular sieve, therefore the method also can cause the reduction of molecular sieve pore passage inner acidic bit quantity when reducing the molecular sieve outer surface acidity bit quantity, for the toluene disproportionation process time, improves when catalyst is selected the type performance the remarkable decline that also can cause catalyst activity.
Therefore, find a kind of efficient oxide modifying micro porous molecular sieve shape-selective catalyst highly significant.
Summary of the invention
The technical problem to be solved in the present invention is loaded down with trivial details for the preparation manipulation of shape-selective catalyst in the synthetic paraxylene process of toluene disproportionation, cost is high, and the problem such as Shape-selective is not high, provides a kind of synthetic method simple, shape-selective catalyst preparation method with low cost, that Shape-selective is high.
The technical solution adopted for the present invention to solve the technical problems is:
The phosphate of 0.11g～2.64g is joined in the 10mL absolute ethyl alcohol, be stirred to and mix; Subsequently the 4g micro porous molecular sieve is added in above-mentioned solution, stir, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains required P
2O
5Modified micropore molecular sieve shape-selective catalyst.
As limitation of the invention, micro porous molecular sieve of the present invention is ZSM-5 or MCM-22; Described phosphate is triethyl phosphate, tricresyl phosphate propyl ester or tributyl phosphate.
As limitation of the invention further, described P
2O
5P in modified micropore molecular sieve shape-selective catalyst
2O
5Content be P
2O
51%～15% of modified micropore molecular sieve shape-selective catalyst catalyst gross mass.
P of the present invention
2O
5Modified micropore molecular sieve shape-selective catalyst can be applied to the toluene disproportionation process.
The phosphate that the present invention adopts, all have larger molecular dimension as triethyl phosphate, tricresyl phosphate propyl ester and tributyl phosphate, and the molecular dimension of this class material obviously is greater than the port size of micro porous molecular sieve, therefore, adopts phosphate as P
2O
5Predecessor by dipping modified micropore molecular sieve, just can effectively avoid traditional and take phosphoric acid and be P
2O
5The problem of predecessor modified micropore molecular sieve shape-selective catalyst preparation process.In dipping process, phosphate mainly is scattered in the micro porous molecular sieve outer surface, so the P generated after roasting
2O
5Also mainly be scattered in molecular sieve outer surface, this not only is conducive to the covering of micro porous molecular sieve outer surface acidity position, also is conducive to the protection of molecule sieve aperture inner acidic position.In the shape selective catalysis process, not only can significantly improve the type of the selecting performance of catalyst, and can keep the activity that catalyst is higher.
The present invention be take first phosphate and is P
2O
5Presoma is carried on the micro porous molecular sieve outer surface by the method for dipping and temperature-programmed calcination by phosphorous oxide; both can effectively cover the acidic site of molecular sieve outer surface; can protect again its inner acidic position, hole unaffected; when maintaining higher catalyst activity, the Shape-selective of catalyst is further improved.Therefore to have the preparation method simple, with low cost in the present invention, the Shape-selective advantages of higher.
The specific embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
The 10mL absolute ethyl alcohol is mixed with 1.13g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 10%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat1.
Embodiment 2
The 10mL absolute ethyl alcohol is mixed with 0.11g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 1%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat2.
Embodiment 3
The 10mL absolute ethyl alcohol is mixed with 1.81g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 15%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat3.
Embodiment 4
The 10mL absolute ethyl alcohol is mixed with 1.81g triethyl phosphate and 4.0g micro porous molecular sieve ZSM-5, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 15%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat4.
Embodiment 5
The 10mL absolute ethyl alcohol is mixed with 1.39g tricresyl phosphate propyl ester and 4.0g micro porous molecular sieve MCM-22, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 10%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat5.
Embodiment 6
The 10mL absolute ethyl alcohol is mixed with 2.64g tributyl phosphate and 4.0g micro porous molecular sieve MCM-22, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 15%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat6.
The comparative example
The phosphate aqueous solution of (0.43mL) 85% and 4.0g micro porous molecular sieve MCM-22 are mixed, be stirred well to and mix, the standing 12h of room temperature; By the material of gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, the speed with 10 ℃/min under air atmosphere is warming up to 600 ℃, and keeps 4h at this temperature, is down to subsequently room temperature and namely obtains 10%P
2O
5Modified micropore molecular sieve shape-selective catalyst.Be designated as Cat7.
By the P obtained in above-described embodiment
2O
5The modified micropore molecular sieve is for the toluene disproportionation process, and the typical reaction condition is: 450 ℃ of reaction temperatures, material quality air speed are 1h
-1, estimate continuously 6h.The catalytic performance of each catalyst is as shown in table 1:
The catalytic performance of table 1 catalyst
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| Cat1 | 24.1 | 71.5 |
| Cat2 | 33.4 | 37.9 |
| Cat3 | 22.8 | 72.2 |
| Cat4 | 23.3 | 70.9 |
| Cat5 | 25.4 | 67.6 |
| Cat6 | 27.9 | 65.5 |
| Cat7 | 6.4 | 62.1 |
The P visible by table 1 result, that the present invention is prepared
2O
5The modified micropore molecular sieve catalyst, to the good catalytic performance of having of toluene disproportionation process, has not only been realized higher toluene conversion, but also has obtained good Shape-selective.With traditional phosphoric acid of take, be P
2O
5The P of predecessor
2O
5The modified micropore molecular sieve catalyst is compared, and the phosphate of take is P
2O
5The P of predecessor
2O
5The modified micropore molecular sieve catalyst shows more excellent catalytic performance to the toluene disproportionation process.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, the relevant staff can, in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on specification, must determine its technical scope according to the claim scope.
Claims (5)
1. P
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst is characterized in that the method carries out according to following step:
(1) 0.11g～2.64g phosphate is joined in the 10mL absolute ethyl alcohol, is stirred to and mixes; Subsequently the micro porous molecular sieve of 4g is added in above-mentioned solution, stir, the standing 12h of room temperature;
(2) by the material of step (1) gained evaporate to dryness in 60 ℃ of water-baths, put into subsequently 120 ℃ of dry 6h of baking oven, transfer in Muffle furnace, speed with 10 ℃/min in air atmosphere is warming up to 600 ℃, and keep 4h at this temperature, and be down to subsequently room temperature, namely obtain required P
2O
5Modified micropore molecular sieve shape-selective catalyst.
2. a kind of P according to claim 1
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst, is characterized in that wherein said micro porous molecular sieve is ZSM-5 or MCM-22.
3. a kind of P according to claim 1
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst, is characterized in that described phosphate is triethyl phosphate, tricresyl phosphate propyl ester or tributyl phosphate.
4. a kind of P according to claim 1
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst, is characterized in that described P
2O
5P in modified micropore molecular sieve shape-selective catalyst
2O
5Negative content be P
2O
51%～15% of modified micropore molecular sieve catalyst gross mass.
5. a kind of P according to claim 1
2O
5The preparation method of modified micropore molecular sieve shape-selective catalyst, is characterized in that described P
2O
5Modified micropore molecular sieve shape-selective catalyst can be used in the toluene disproportionation process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437600A (en) * | 2014-09-29 | 2015-03-25 | 常州大学 | Method for preparing phosphorus oxide modified microporous molecular sieve shape-selective catalyst |
| CN104492478A (en) * | 2014-11-21 | 2015-04-08 | 常州大学 | Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst |
| CN106582786A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Preparation method of boron modification microporous molecular sieve shape-selective catalyst |
| CN109569718A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method of melem modified micropore molecular sieve shape-selective catalyst |
| CN109569702A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method and application of carbonitride modified micropore molecular sieve shape-selective catalyst |
| CN115888800A (en) * | 2022-09-22 | 2023-04-04 | 河南永大化工科技有限公司 | Shape-selective catalyst for p-diethylbenzene and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437600A (en) * | 2014-09-29 | 2015-03-25 | 常州大学 | Method for preparing phosphorus oxide modified microporous molecular sieve shape-selective catalyst |
| CN104492478A (en) * | 2014-11-21 | 2015-04-08 | 常州大学 | Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst |
| CN106582786A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Preparation method of boron modification microporous molecular sieve shape-selective catalyst |
| CN109569718A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method of melem modified micropore molecular sieve shape-selective catalyst |
| CN109569702A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method and application of carbonitride modified micropore molecular sieve shape-selective catalyst |
| CN115888800A (en) * | 2022-09-22 | 2023-04-04 | 河南永大化工科技有限公司 | Shape-selective catalyst for p-diethylbenzene and preparation method and application thereof |
| CN115888800B (en) * | 2022-09-22 | 2024-05-24 | 河南永大化工科技有限公司 | Shape-selective catalyst for diethylbenzene and preparation method and application thereof |
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