CN103406142B - A kind of P 2o 5the preparation method of modified micropore molecular sieve shape-selective catalyst - Google Patents
A kind of P 2o 5the preparation method of modified micropore molecular sieve shape-selective catalyst Download PDFInfo
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- CN103406142B CN103406142B CN201310302211.6A CN201310302211A CN103406142B CN 103406142 B CN103406142 B CN 103406142B CN 201310302211 A CN201310302211 A CN 201310302211A CN 103406142 B CN103406142 B CN 103406142B
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- molecular sieve
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Abstract
The present invention relates to a kind of P
2o
5the preparation method of modified micropore molecular sieve shape-selective catalyst, the method for matrix, is that presoma passes through the method for dipping and temperature-programmed calcination by P with micro porous molecular sieve ZSM-5 or MCM-22 with phosphate
2o
5be carried on micro porous molecular sieve outer surface, P in shape-selective catalyst
2o
5content be 1% ~ 15% of catalyst gross mass.The shape-selective catalyst that the present invention obtains has good shape selective catalysis performance to toluene disproportionation procedure, and method for preparing catalyst is simple.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, particularly a kind of P for toluene disproportionation synthesis paraxylene process
2o
5the preparation method of modified micropore molecular sieve shape-selective catalyst.
Background technology
The process of toluene disproportionation synthesis paraxylene is typical shape selective catalysis process.Micro porous molecular sieve such as ZSM-5 and MCM-22 is the shape-selective catalyst that toluene disproportionation procedure is conventional.But, because these micro porous molecular sieve outer surfaces have a large amount of acidic site, this is easy to, on the acidic site of molecular sieve outer surface, isomerization reaction occurs with regard to causing the paraxylene generated in molecular sieve pore passage in toluene disproportionation procedure, thus reduces 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 in order to 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 effectively can 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 good effect, therefore operate more loaded down with trivial details, energy consumption is higher.Pre-carbon distribution also can improve the Shape-selective of molecular sieve catalyst, but also must carry out again pre-carbon distribution due to the catalyst after regeneration, therefore operates loaded down with trivial details, and is also only limitted to laboratory research at present.
Adopt oxide modifying to cover the operation of molecular sieve outer surface acidity position very simply, and once just can complete good covering.Conventional P
2o
5modified micropore molecular sieve shape-selective catalyst often adopts phosphoric acid as P
2o
5predecessor, and phosphoric acid is not only scattered in 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 while reducing molecular sieve outer surface acidity bit quantity, improves the remarkable decline that also can cause catalyst activity while type performance selected by catalyst time in for toluene disproportionation procedure.
Therefore, a kind of oxide modifying micro porous molecular sieve shape-selective catalyst is efficiently found 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 toluene disproportionation synthesis paraxylene process, cost is high, and the problem such as Shape-selective is not high, provides a kind of synthetic method simple, with low cost, the shape-selective catalyst preparation method 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 10mL absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by 4g micro porous molecular sieve subsequently, stir, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 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 toluene disproportionation procedure.
The phosphate that the present invention adopts, as triethyl phosphate, tricresyl phosphate propyl ester and tributyl phosphate all have larger molecular dimension, and the molecular dimension of this kind of material is obviously greater than the port size of micro porous molecular sieve, therefore, adopts phosphate as P
2o
5predecessor just can effectively to avoid traditional by dipping modified micropore molecular sieve be P with phosphoric acid
2o
5the problem of predecessor modified micropore molecular sieve shape-selective catalyst preparation process.In dipping process, phosphate is mainly scattered in micro porous molecular sieve outer surface, the P therefore generated after roasting
2o
5also be mainly scattered in molecular sieve outer surface, this is not only conducive to the covering of micro porous molecular sieve outer surface acidity position, is also conducive to the protection of molecular sieve pores inner acidic position.In shape selective catalysis process, not only can significantly improve type of the selecting performance of catalyst, and the activity that catalyst is higher can be kept.
The present invention is P first with phosphate
2o
5phosphorous oxide is carried on micro porous molecular sieve outer surface by the method for dipping and temperature-programmed calcination by presoma; both the acidic site of molecular sieve outer surface can effectively have been covered; its inner acidic position, hole can be protected again unaffected; while the catalyst activity that maintenance is higher, the Shape-selective of catalyst is improved further.Therefore the present invention has preparation method simply, with low cost, Shape-selective advantages of higher.
Detailed description of the invention
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
Embodiment 1
Mixed with 1.13g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 10%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat1.
Embodiment 2
Mixed with 0.11g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 1%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat2.
Embodiment 3
Mixed with 1.81g triethyl phosphate and 4.0g micro porous molecular sieve MCM-22 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 15%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat3.
Embodiment 4
Mixed with 1.81g triethyl phosphate and 4.0g micro porous molecular sieve ZSM-5 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 15%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat4.
Embodiment 5
Mixed with 1.39g tricresyl phosphate propyl ester and 4.0g micro porous molecular sieve MCM-22 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 10%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat5.
Embodiment 6
Mixed with 2.64g tributyl phosphate and 4.0g micro porous molecular sieve MCM-22 by 10mL absolute ethyl alcohol, be stirred well to and mix, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 15%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat6.
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, room temperature leaves standstill 12h; By the material of gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently and namely obtain 10%P
2o
5modified micropore molecular sieve shape-selective catalyst.Be designated as Cat7.
By the P obtained in above-described embodiment
2o
5modified micropore molecular sieve is used in toluene disproportionation procedure, and typical reaction condition is: reaction temperature 450 DEG C, and material quality air speed is 1h
-1, evaluate 6h continuously.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 |
From table 1 result, the P prepared by the present invention
2o
5modified micropore molecular sieve catalyst has good catalytic performance to toluene disproportionation procedure, not only achieves higher toluene conversion, but also obtains good Shape-selective.With traditional take phosphoric acid as P
2o
5the P of predecessor
2o
5modified micropore molecular sieve catalyst is compared, and take phosphate as P
2o
5the P of predecessor
2o
5modified micropore molecular sieve catalyst shows more excellent catalytic performance to toluene disproportionation procedure.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (4)
1. a P
2o
5the preparation method of modified micropore molecular sieve shape-selective catalyst, is characterized in that the method is carried out according to following step:
(1) by 0.11g ~ 2.64g triethyl phosphate, tricresyl phosphate propyl ester or tributyl phosphate join in 10mL absolute ethyl alcohol, are stirred to and mix; Added in above-mentioned solution by the micro porous molecular sieve of 4g subsequently, stir, room temperature leaves standstill 12h;
(2) by the material of step (1) gained evaporate to dryness in 60 DEG C of water-baths, put into 120 DEG C of dry 6h of baking oven subsequently, transfer in Muffle furnace, 600 DEG C are warming up to the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, be down to room temperature subsequently, 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 P
2o
5p in modified micropore molecular sieve shape-selective catalyst
2o
5load capacity be P
2o
51% ~ 15% of modified micropore molecular sieve catalyst gross mass.
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
5modified micropore molecular sieve shape-selective catalyst can be used in toluene disproportionation procedure.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437600B (en) * | 2014-09-29 | 2016-08-03 | 常州大学 | A kind of preparation method of phosphorous oxides modified micropore 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 |
| CN109569718B (en) * | 2018-12-05 | 2021-01-26 | 常州大学 | Preparation method of melem modified microporous 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 |
| 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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| EP0089787A2 (en) * | 1982-03-18 | 1983-09-28 | Mobil Oil Corporation | Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion |
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| CN102050458A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Modified molecular sieve capable of improving sodium pollution resisting capability and preparation method of modified molecular sieve |
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| EP0089787A2 (en) * | 1982-03-18 | 1983-09-28 | Mobil Oil Corporation | Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion |
| CN85102828A (en) * | 1985-04-01 | 1986-07-23 | 大连工学院 | Produce p-methyl-ethylbenzene with phosphorous modified ZSM-5 catalyst |
| CN101711992A (en) * | 2008-09-29 | 2010-05-26 | 宁夏大学 | Catalyst for selectively producing propene by methanol or dimethyl ether and preparation method thereof |
| CN102050458A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Modified molecular sieve capable of improving sodium pollution resisting capability and preparation method of modified molecular sieve |
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