CN104437600B - A kind of preparation method of phosphorous oxides modified micropore molecular sieve shape-selective catalyst - Google Patents
A kind of preparation method of phosphorous oxides modified micropore molecular sieve shape-selective catalyst Download PDFInfo
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- CN104437600B CN104437600B CN201410516173.9A CN201410516173A CN104437600B CN 104437600 B CN104437600 B CN 104437600B CN 201410516173 A CN201410516173 A CN 201410516173A CN 104437600 B CN104437600 B CN 104437600B
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Abstract
The present invention relates to the preparation method of a kind of phosphorous oxides modified micropore molecular sieve shape-selective catalyst, the method is with micro porous molecular sieve ZSM 5 or MCM 22 as matrix, by the method for dipping and temperature-programmed calcination, phosphorous oxides being carried on micro porous molecular sieve outer surface with pyrophosphorous acid, hypophosphoric acid, different hypophosphoric acid, pyrophosphoric acid, triphosphoric acid or the perphosphoric acid presoma as phosphorous oxides, wherein phosphorous oxides is 1:6 1:20 with the mass ratio of micro porous molecular sieve.The shape-selective catalyst that the present invention obtains has good shape selective catalysis performance to toluene disproportionation and ethylbenzene disproportionation process, and method for preparing catalyst is simple.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, particularly to one for toluene disproportionation and
The preparation method of the phosphorous oxides modified micropore molecular sieve shape-selective catalyst of ethylbenzene disproportionation process.
Background technology
Toluene disproportionation and ethylbenzene disproportionation are synthesis xylol and the key industry production process of p-Diethylbenzene, all
It it is typical shape selective catalysis process.Micro porous molecular sieve such as ZSM-5 and MCM-22 is toluene disproportionation or ethylbenzene
The shape-selective catalyst that dismutation is conventional.But, owing to these micro porous molecular sieve outer surfaces have a large amount of acidic site,
This results in the xylol generated in molecular sieve pore passage in toluene disproportionation procedure and is easy in molecular sieve appearance
There is isomerization reaction on the acidic site in face, thus reduce the selectivity of para-position product.For high selectivity
The xylol that obtains be necessary for being modified reducing the quantity of its outer surface acidity position to micro porous molecular sieve.
Common method of modifying has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre-carbon distribution and metal-oxide to change
Property.Although the method for siliceous deposits can be effectively improved the Shape-selective of molecular sieve catalyst, but due to molecular sieve
Active force between surface hydroxyl and deposit is the most weak, and the deposition generally requiring 3～4 times can be only achieved preferably
Effect, therefore operates comparatively laborious, and energy consumption is higher.Pre-carbon distribution can also improve the shape-selective of molecular sieve catalyst
Performance, but owing to the catalyst after regeneration must also carry out the most pre-carbon distribution, therefore operate loaded down with trivial details, and
Currently also it is only limitted to laboratory research.
Use oxide modifying, especially phosphorous oxides modified, cover the behaviour of molecular sieve outer surface acidity position
Make very simple, and the most just can complete preferably to cover.Tradition phosphorous oxides modified micropore molecular sieve
Shape-selective catalyst often use phosphoric acid or ammonium dihydrogen phosphate as the predecessor of phosphorous oxides, and phosphoric acid or phosphoric acid
Ammonium dihydrogen is not only scattered in micro porous molecular sieve outer surface in dipping process, also can be scattered in micro porous molecular sieve
In duct, therefore the method also can cause molecular sieve pores while reducing molecular sieve outer surface acidity bit quantity
The reduction of road inner acidic bit quantity, improves in course of reaction time while type performance selected by catalyst and also can
Cause being remarkably decreased of catalyst activity.Also researcher is had to be used for as the predecessor of phosphorous oxides by phosphate ester
The preparation of phosphorous oxides modified micropore molecular sieve shape-selective catalyst (Chinese invention patent, application number:
201310312211.6).The method uses the phosphate ester that molecular dimension is bigger, such as triethyl phosphate, tricresyl phosphate
Propyl ester or tributyl phosphate, prepare for the predecessor of phosphorous oxides that phosphorous oxides modified micropore molecular sieve is shape-selective urges
Agent.Although this method overcomes tradition prepares phosphorous oxides modified micropore molecular sieve shape selective catalysis agent method
The problem of (using phosphoric acid or ammonium dihydrogen phosphate as the predecessor of phosphorous oxides) (causes molecular sieve pores inner acidic
Position is covered by phosphorous oxides), but there is also some problems: as phosphate ester is to water sensitive, in preparation process
Meet water can decompose, thus cause molecular sieve pore passage to be blocked；The most such as, drying course easily causes part
Phosphate ester volatilizees and cannot accurately estimate the problems such as actual phosphorous oxides load capacity.
Therefore, find a kind of phosphorous oxides modified micropore molecular sieve shape-selective catalyst convenient, efficient to have a mind to very much
Justice.
Summary of the invention
The technical problem to be solved in the present invention is to synthesize xylol and to two for toluene disproportionation and ethylbenzene disproportionation
During ethylbenzene, the preparation manipulation of shape-selective catalyst is loaded down with trivial details, condition harshness and high in cost of production problem, it is provided that a kind of
Synthetic method is simple, with low cost, the preparation method of the shape-selective catalyst that Shape-selective is high.
The technical solution adopted for the present invention to solve the technical problems is:
Phosphorous oxides predecessor is added in absolute methanol, wherein phosphorous oxides predecessor and the mass ratio of methanol
For 1:5-1:10, stirring is to being completely dissolved；Subsequently micro porous molecular sieve is added in above-mentioned solution, wherein phosphorus oxidation
Thing is 1:6-1:20 with the mass ratio of micro porous molecular sieve, stirs, and room temperature stands 12h；By the material of gained
It is evaporated in a water bath, is subsequently placed in 120 DEG C of baking ovens and is dried 6h, transfer in Muffle furnace, at air gas
Atmosphere is warming up to 600 DEG C with the speed of 10 DEG C/min, and keeps 4h at this temperature, be subsequently reduced to room temperature,
I.e. obtain required phosphorous oxides modified 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；Institute
The phosphorous oxides predecessor stated is pyrophosphorous acid, hypophosphoric acid, different hypophosphoric acid, pyrophosphoric acid, triphosphoric acid or
Perphosphoric acid.
Phosphorous oxides modified micropore molecular sieve shape-selective catalyst of the present invention can apply to toluene disproportionation and
Ethylbenzene disproportionation process.
The phosphorous oxides predecessor that the present invention uses, such as pyrophosphorous acid, hypophosphoric acid, different hypophosphoric acid, Jiao
Phosphoric acid, triphosphoric acid or perphosphoric acid, all have bigger molecular dimension, be shown below:
The molecular dimension of this kind of material is significantly greater than the port size of micro porous molecular sieve, therefore, uses above-mentioned thing
Matter just can be prevented effectively from tradition with phosphoric acid as the predecessor of phosphorous oxides by dipping modified micropore molecular sieve
Or the problem that ammonium dihydrogen phosphate is phosphorous oxides predecessor modified micropore molecular sieve shape-selective catalyst preparation process.
In dipping process, above-mentioned phosphorous oxides predecessor can only be scattered in micro porous molecular sieve outer surface, therefore raw after roasting
The phosphorous oxides become also can only be scattered in molecular sieve outer surface, and this not only contributes to the acid of micro porous molecular sieve outer surface
The covering of property position, is also beneficial to the protection of molecular sieve pores inner acidic position.During shape selective catalysis, not only may be used
To significantly improve type of the selecting performance of catalyst, and the activity that catalyst is higher can be kept.With phosphate ester,
Such as triethyl phosphate, tricresyl phosphate propyl ester or tributyl phosphate, the phosphorus oxygen prepared as the predecessor of phosphorous oxides
Compound modified micropore molecular sieve shape-selective catalyst is compared, and method more convenient operation proposed by the invention, to system
Standby condition requires milder, especially the highest to environment steam content requirement, and this for industrialization amplification is all
Very advantageously.
The present invention is first with pyrophosphorous acid, hypophosphoric acid, different hypophosphoric acid, pyrophosphoric acid, triphosphoric acid or excessively two
Phosphoric acid is phosphorous oxides presoma to be carried on micropore by the method for dipping and temperature-programmed calcination by phosphorous oxide and divides
Son sieve outer surface, both can effectively cover the acidic site of molecular sieve outer surface, can protect again its hole inner acidic
Position is unaffected, while maintaining higher catalyst activity, makes the Shape-selective of catalyst significantly improve.
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 example, however, it should be noted that these embodiments only as a example by
Show purposes of discussion, and be not necessarily to be construed as the restriction that the present invention implements.
Embodiment 1
Being added by hypophosphoric acid in absolute methanol, wherein hypophosphoric acid is 1:5 with the mass ratio of methanol, and stirring is extremely
It is completely dissolved；Being added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, wherein hypophosphoric acid divides with micropore
The mass ratio of son sieve is 1:20, stirs, and room temperature stands 12h；Gained material is evaporated in a water bath, with
After put in 120 DEG C of baking ovens be dried 6h, transfer in Muffle furnace, with 10 DEG C/min's in air atmosphere
Speed is warming up to 600 DEG C, and keeps 4h at this temperature, is subsequently reduced to room temperature, i.e. obtains required phosphorus oxygen
Compound modified micropore molecular sieve shape-selective catalyst, is designated as Cat1.
Embodiment 2
Being added by pyrophosphoric acid in absolute methanol, wherein pyrophosphoric acid is 1:7 with the mass ratio of methanol, and stirring is to completely
Dissolve；Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein pyrophosphoric acid and micro porous molecular sieve
Mass ratio is 1:6, stirs, and room temperature stands 12h；Gained material is evaporated in a water bath, is subsequently placed into
120 DEG C of baking ovens are dried 6h, transfer in Muffle furnace, with the speed liter of 10 DEG C/min in air atmosphere
Temperature is to 600 DEG C, and keeps 4h at this temperature, is subsequently reduced to room temperature, i.e. obtains required phosphorous oxides and change
Property micro porous molecular sieve shape-selective catalyst, is designated as Cat2.
Embodiment 3
Being added by pyrophosphorous acid in absolute methanol, wherein pyrophosphorous acid is 1:10 with the mass ratio of methanol, stirring
To being completely dissolved；Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein pyrophosphorous acid and micropore
The mass ratio of molecular sieve is 1:6, stirs, and room temperature stands 12h；Gained material is evaporated in a water bath,
It is subsequently placed in 120 DEG C of baking ovens and is dried 6h, transfer in Muffle furnace, with 10 DEG C/min in air atmosphere
Speed be warming up to 600 DEG C, and keep 4h at this temperature, be subsequently reduced to room temperature, i.e. obtain required phosphorus
Oxide modifying micro porous molecular sieve shape-selective catalyst, is designated as Cat3.
Embodiment 4
Being added by different hypophosphoric acid in absolute methanol, the most different hypophosphoric acid is 1:10 with the mass ratio of methanol,
Stirring is to being completely dissolved；Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, the most different hypophosphoric acid
Being 1:10 with the mass ratio of micro porous molecular sieve, stir, room temperature stands 12h；By gained material in a water bath
Be evaporated, be subsequently placed in 120 DEG C of baking ovens be dried 6h, transfer in Muffle furnace, in air atmosphere with
The speed of 10 DEG C/min is warming up to 600 DEG C, and keeps 4h at this temperature, is subsequently reduced to room temperature, i.e. obtains
Required phosphorous oxides modified micropore molecular sieve shape-selective catalyst, is designated as Cat4.
Embodiment 5
Being added by triphosphoric acid in absolute methanol, wherein triphosphoric acid is 1:6 with the mass ratio of methanol, and stirring is to completely
Dissolve；Subsequently micro porous molecular sieve MCM-22 is added in above-mentioned solution, wherein triphosphoric acid and micro porous molecular sieve
Mass ratio be 1:6, stir, room temperature stand 12h；Gained material is evaporated in a water bath, puts subsequently
Enter and 120 DEG C of baking ovens are dried 6h, transfer in Muffle furnace, with the speed of 10 DEG C/min in air atmosphere
It is warming up to 600 DEG C, and keeps 4h at this temperature, be subsequently reduced to room temperature, i.e. obtain required phosphorous oxides
Modified micropore molecular sieve shape-selective catalyst, is designated as Cat5.
Embodiment 6
Being added by perphosphoric acid in absolute methanol, wherein perphosphoric acid is 1:10 with the mass ratio of methanol, stirring
To being completely dissolved；Being added in above-mentioned solution by micro porous molecular sieve MCM-22 subsequently, wherein perphosphoric acid is with micro-
The mass ratio of porous molecular sieve is 1:15, stirs, and room temperature stands 12h；Gained material is evaporated in a water bath,
It is subsequently placed in 120 DEG C of baking ovens and is dried 6h, transfer in Muffle furnace, with 10 DEG C/min in air atmosphere
Speed be warming up to 600 DEG C, and keep 4h at this temperature, be subsequently reduced to room temperature, i.e. obtain required phosphorus
Oxide modifying micro porous molecular sieve shape-selective catalyst, is designated as Cat6.
Comparative example
Being added by phosphoric acid in absolute methanol, wherein phosphoric acid is 1:10 with the mass ratio of methanol, and stirring is to the most molten
Solve；Subsequently micro porous molecular sieve MCM-22 is added in above-mentioned solution, wherein phosphorous oxides and micro porous molecular sieve
Mass ratio be 1:6, stir, room temperature stand 12h；Gained material is evaporated in a water bath, puts subsequently
Enter and 120 DEG C of baking ovens are dried 6h, transfer in Muffle furnace, with the speed of 10 DEG C/min in air atmosphere
It is warming up to 600 DEG C, and keeps 4h at this temperature, be subsequently reduced to room temperature, i.e. obtain required phosphorous oxides
Modified micropore molecular sieve shape-selective catalyst, is designated as Cat7.
The phosphorous oxides modified micropore molecular sieve obtained in above-described embodiment is used in toluene disproportionation procedure,
Type reaction condition is: reaction temperature 450 DEG C, and raw materials quality air speed is 1h-1, evaluate 6h continuously.Respectively urge
The catalytic performance of agent is as shown in table 1:
The catalytic performance of table 1 catalyst
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| Cat1 | 35.2 | 69.6 |
| Cat2 | 28.1 | 77.8 |
| Cat3 | 27.6 | 79.1 |
| Cat4 | 32.9 | 72.6 |
| Cat5 | 30.7 | 82.4 |
| Cat6 | 27.1 | 57.4 |
| Cat7 | 7.3 | 65.9 |
During the phosphorous oxides modified micropore molecular sieve obtained in above-described embodiment is used for ethylbenzene disproportionation,
Type reaction condition is: reaction temperature 400 DEG C, and raw materials quality air speed is 1h-1, evaluate 6h continuously.Respectively urge
The catalytic performance of agent is as shown in table 2:
The catalytic performance of table 2 catalyst
| Catalyst | Conversion of ethylbenzene (%) | P-Diethylbenzene selectivity (%) |
| Cat1 | 35.1 | 84.6 |
| Cat2 | 30.7 | 95.8 |
| Cat3 | 31.4 | 96.2 |
| Cat4 | 33.6 | 90.7 |
| Cat5 | 37.1 | 97.5 |
| Cat6 | 33.2 | 74.8 |
| Cat7 | 11.3 | 82.7 |
From Tables 1 and 2 result, the phosphorous oxides modified micropore molecular sieve catalyst prepared by the present invention
Toluene disproportionation and ethylbenzene disproportionation process there are is good catalytic performance, not only achieve higher conversion ratio,
But also obtain good Shape-selective.With traditional modified micropore being phosphorous oxides predecessor with phosphoric acid
Molecular sieve catalyst is compared, and the phosphorous oxides modified micropore molecular sieve catalyst prepared by the present invention is to toluene discrimination
Change and ethylbenzene disproportionation process shows more excellent shape selective catalysis performance.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, related work
Personnel can carry out various change and amendment completely in the range of without departing from this invention technological thought.
The content that the technical scope of this invention is not limited in description, it is necessary to according to right
Determine its technical scope.
Claims (4)
1. the preparation method of a phosphorous oxides modified micropore molecular sieve shape-selective catalyst, it is characterised in that the party
Method is carried out as steps described below:
(1) adding in absolute methanol by phosphorous oxides predecessor, micropore, to being completely dissolved, is divided by stirring subsequently
Stirring in the son sieve above-mentioned solution of addition, room temperature stands 12h, and wherein said phosphorous oxides predecessor is burnt
Phosphorous acid, hypophosphoric acid, different hypophosphoric acid, pyrophosphoric acid, triphosphoric acid or perphosphoric acid；
(2) material of step (1) gained is evaporated in a water bath, is subsequently placed in 120 DEG C of baking ovens and is dried
6h, transfers in Muffle furnace, is warming up to 600 DEG C with the speed of 10 DEG C/min in air atmosphere, and
Keep 4h at a temperature of this, be subsequently reduced to room temperature, i.e. obtain required phosphorous oxides modified micropore molecular sieve shape-selective
Catalyst.
The preparation of a kind of phosphorous oxides modified micropore molecular sieve shape-selective catalyst the most according to claim 1
Method, it is characterised in that the phosphorous oxides predecessor described in step (1) with the mass ratio of absolute methanol is
1:5-1:10, phosphorous oxides predecessor is 1:6-1:20 with the mass ratio of micro porous molecular sieve.
The preparation of a kind of phosphorous oxides modified micropore molecular sieve shape-selective catalyst the most according to claim 1
Method, it is characterised in that described micro porous molecular sieve is ZSM-5 or MCM-22.
The preparation of a kind of phosphorous oxides modified micropore molecular sieve shape-selective catalyst the most according to claim 1
Method, it is characterised in that described phosphorous oxides modified micropore molecular sieve shape-selective catalyst can be used for toluene disproportionation
During ethylbenzene disproportionation.
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