CN104607236B - Preparation method of catalyst for toluene disproportionation process - Google Patents
Preparation method of catalyst for toluene disproportionation process Download PDFInfo
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- CN104607236B CN104607236B CN201510077043.4A CN201510077043A CN104607236B CN 104607236 B CN104607236 B CN 104607236B CN 201510077043 A CN201510077043 A CN 201510077043A CN 104607236 B CN104607236 B CN 104607236B
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- catalyst
- molecular sieve
- barium
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- toluene disproportionation
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Abstract
The invention relates to a preparation method of a catalyst for a toluene disproportionation process. The method comprises the following step of grinding and roasting by taking a microporous molecular sieve ZSM-5 or MCM-22 as a carrier and taking barium nitrate, barium carbonate or barium acetate as a barium oxide precursor. By the method, the acid site of the outer surface of the microporous molecular sieve is covered without affecting the acid property in pores of the microporous molecular sieve. The catalyst obtains a relatively good shape selection effect when being used for toluene disproportionation for synthesizing the paraxylene. The preparation method of the catalyst is simple and energy-saving, and shape selection effect of the catalyst is good.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, more particularly to a kind of to synthesize to two for toluene disproportionation
The preparation method of the Barium monoxide modified micropore molecular sieve shape-selective catalyst of toluene process.
Background technology
The process for synthesizing xylol by toluene disproportionation is typical shape selective catalysis process.Common micro porous molecular sieve is such as
ZSM-5 and MCM-22 are the conventional shape-selective catalysts of toluene disproportionation procedure.However, because these micro porous molecular sieve outer surfaces have
A large amount of acidic sites, this results in the xylol generated in molecular sieve pore passage in toluene disproportionation procedure and is easy to outside molecular sieve
There is isomerization reaction on the acidic site on surface, so as to reduce the selectivity of para-position product.Obtain right for high selectivity
Dimethylbenzene just must be modified to reduce the quantity of its outer surface acidity position to micro porous molecular sieve.Common having of method of modifying
Learn gas phase siliceous deposits, chemical liquid phase siliceous deposits, pre- carbon distribution and metal oxide modified.Although the method for siliceous deposits can be carried effectively
The Shape-selective of macromolecule sieve catalyst, but because the active force between molecular sieve surface hydroxyl and deposit is very weak, often need
The deposition for wanting 3～4 times can be only achieved preferable effect, therefore operation is comparatively laborious, and energy consumption is higher.Pre- carbon distribution can also be improved point
The Shape-selective of sub- sieve catalyst, but because the catalyst after regeneration must also carry out pre- carbon distribution again, therefore operation is loaded down with trivial details,
And also it is only limitted to laboratory research at present.
Molecular sieve outer surface acidity bit manipulation is covered using metal oxide modified very simple, and once just can be with
Preferable coverage effect is completed, but the method can also cause reduction acid in duct while outer surface acidity is reduced, because
This also fails to large-scale use.Patent (CN102513144B) prepares metal oxide modified micropore using the method for complexation dipping
Molecular sieve shape-selective catalyst, although achieve preferable shape-selective effect (Selectivity for paraxylene reaches 81.2%), but distance
Also there is a big difference for application requirement (Selectivity for paraxylene is higher than 90%)；Patent (CN102872901A) using complexation dipping with
The method that conventional impregnation combines improves the selectivity of para-position product, and Selectivity for paraxylene had once been up to 87.3%.But this
Kind of method prepare shape-selective catalyst need to impregnate micro porous molecular sieve twice, dry, the process such as roasting, cumbersome, consumption
Can be time-consuming.Therefore in the urgent need to one kind is simple to operate, the high molecular sieve modified method of with low cost and Shape-selective is applied to
In the building-up process of xylol.Therefore, a kind of efficient oxide modifying micro porous molecular sieve shape-selective catalyst is found very intentional
Justice.
The content of the invention
Shape-selective catalyst for toluene disproportionation procedure of the present invention is with barium nitrate, brium carbonate or barium acetate as oxygen
Change barium precursor, with micro porous molecular sieve as carrier, prepared by the method for grinding and roasting.
What the method was specifically implemented according to following steps：(1) Barium monoxide predecessor and micro porous molecular sieve are added to into agate
In Nao mortars and it is ground to uniform；(2) material in step (1) is put in Muffle furnace, 600 is warming up in air atmosphere
DEG C, be subsequently reduced to room temperature, that is, obtain required catalyst.Barium monoxide is with the mass ratio in micro porous molecular sieve in gained catalyst
1:3～1:15.
Used as limitation of the invention, heretofore described micro porous molecular sieve is ZSM-5 or MCM-22.
The present invention adopts grinding and the mode of roasting to be prepared for barium nitrate, brium carbonate or barium acetate as predecessor Barium monoxide
Modified micropore molecular sieve shape-selective catalyst, effectively overcomes conventional oxide modified micropore molecular sieve shape-selective catalyst preparation process
In many deficiencies：First, the preparation procedure of catalyst is simplified, artificial and energy consumption has been saved.Compared with traditional infusion process,
Method of the present invention only with heating up roasting after mechanical lapping mixing, with traditional dipping, drying, roasting process phase
Than the preparation procedure that enormously simplify catalyst；Secondly, the Barium monoxide that effective control is generated is to acid in microporous molecular sieve aperture
The impact of position.Disperse power of the present invention for Barium monoxide predecessor on micro porous molecular sieve surface is only mechanical lapping, due to micro-
There is capillary effect in porous molecular sieve hole, therefore the Barium monoxide predecessor of solid-state cannot be diffused in microporous molecular sieve aperture
, therefore, it can only be scattered in micro porous molecular sieve outer surface, so as to reduce the impact to acidic site in microporous molecular sieve aperture.
It is based on above-mentioned reason so that Barium monoxide modified micropore molecular sieve shape-selective catalyst proposed by the invention is in ethylbenzene disproportionation mistake
Only not good shape-selective effect in journey, but also show good catalysis activity.
In sum, catalyst of the present invention has preparation method simple, and with low cost, Shape-selective height etc. is excellent
Point.
Specific embodiment
The present invention will be described further with regard to following examples, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the restriction of present invention enforcement.
Embodiment 1
0.34g barium nitrates and 3g micro porous molecular sieve ZSM-5 are added in agate mortar and are ground to uniformly, subsequently by institute
Obtain material to be put in Muffle furnace, 600 DEG C are warming up in air atmosphere, be subsequently reduced to room temperature, that is, obtain required catalyst.Institute
It is 1 to obtain Barium monoxide and the mass ratio in micro porous molecular sieve in catalyst:15.The catalyst is designated as CAT-1
Embodiment 2
0.51 barium nitrate and 3g micro porous molecular sieve ZSM-5 are added in agate mortar and are ground to uniformly, subsequently by institute
Obtain material to be put in Muffle furnace, 600 DEG C are warming up in air atmosphere, be subsequently reduced to room temperature, that is, obtain required catalyst.Institute
It is 1 to obtain Barium monoxide and the mass ratio in micro porous molecular sieve in catalyst:10.The catalyst is designated as CAT-2
Embodiment 3
1.7g barium nitrates and 3g micro porous molecular sieve ZSM-5 are added in agate mortar and are ground to uniformly, subsequently by institute
Obtain material to be put in Muffle furnace, 600 DEG C are warming up in air atmosphere, be subsequently reduced to room temperature, that is, obtain required catalyst.Institute
It is 1 to obtain Barium monoxide and the mass ratio in micro porous molecular sieve in catalyst:3.The catalyst is designated as CAT-3
Embodiment 4
0.42g barium acetates and 3g micro porous molecular sieve MCM-22 are added in agate mortar and are ground to uniformly, subsequently will
Gained material is put in Muffle furnace, and 600 DEG C are warming up in air atmosphere, is subsequently reduced to room temperature, that is, obtain required catalyst.
Barium monoxide and the mass ratio in micro porous molecular sieve are 1 in gained catalyst:12.The catalyst is designated as CAT-4
Embodiment 5
0.32g brium carbonates and 3g micro porous molecular sieve MCM-22 are added in agate mortar and are ground to uniformly, subsequently will
Gained material is put in Muffle furnace, and 600 DEG C are warming up in air atmosphere, is subsequently reduced to room temperature, that is, obtain required catalyst.
Barium monoxide and the mass ratio in micro porous molecular sieve are 1 in gained catalyst:12.The catalyst is designated as CAT-5
Comparative example 1
Weigh a certain amount of 1.7g barium nitrates, in adding it to 10mL deionized waters, after barium nitrate is completely dissolved again to
3g micro porous molecular sieve MCM-22 are added in the aqueous solution of barium nitrate, is stirred, be stored at room temperature after 24h and be transferred to air dry oven
In 110 DEG C be dried 6h, place into roasting in Muffle furnace, be warming up to 600 DEG C, be subsequently reduced to room temperature.Barium monoxide in gained catalyst
It is 1 with the mass ratio in micro porous molecular sieve:3.The catalyst is designated as CAT-6
During catalyst in above-described embodiment is applied to into toluene disproportionation synthesis xylol, reaction condition is such as
Under：420 DEG C of reaction temperature, raw materials quality air speed is 1h-1。
Its catalytic performance is as shown in table 1：
The catalytic performance of catalyst
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| CAT-1 | 35.7 | 79.2 |
| CAT-2 | 30.4 | 86.5 |
| CAT-3 | 24.9 | 95.1 |
| CAT-4 | 27.6 | 90.3 |
| CAT-5 | 22.7 | 88.2 |
| CAT-6 | 8.2 | 81.9 |
As can be seen from the above table, catalyst of the present invention is applied in the building-up process of xylol, to diformazan
The selectivity of benzene reaches as high as 95.1%, has reached good shape-selective effect；And the method for preparing catalyst of the present invention is simple,
It is with low cost, it is a kind of preferably catalyst with high Shape-selective.
With the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Entirely various change and modification can be carried out in the range of without departing from this invention technological thought.The technology of this invention
Property scope is not limited to the content in description, it is necessary to its technical scope is determined according to right.
Claims (4)
1. a kind of preparation method for toluene disproportionation procedure catalyst, it is characterised in that the method is to implement as steps described below
's：
(1) Barium monoxide predecessor and micro porous molecular sieve are put in agate mortar and are ground to uniformly；
(2) material obtained by step (1) is put in Muffle furnace, 600 DEG C is warming up in air atmosphere, be subsequently reduced to room temperature,
Obtain required catalyst.
2. a kind of preparation method for toluene disproportionation procedure catalyst according to claim 1, it is characterised in that described
Catalyst in the mass ratio of Barium monoxide and micro porous molecular sieve be 1:3～1:15.
3. a kind of preparation method for toluene disproportionation procedure catalyst according to claim 1 and 2, it is characterised in that institute
The micro porous molecular sieve stated is ZSM-5 or MCM-22.
4. a kind of preparation method for toluene disproportionation procedure catalyst according to claim 1 and 2, it is characterised in that institute
The Barium monoxide predecessor stated is barium nitrate, brium carbonate or barium acetate.
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| CN201510077043.4A CN104607236B (en) | 2015-02-12 | 2015-02-12 | Preparation method of catalyst for toluene disproportionation process |
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| CN201510077043.4A CN104607236B (en) | 2015-02-12 | 2015-02-12 | Preparation method of catalyst for toluene disproportionation process |
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| CN104607236B true CN104607236B (en) | 2017-04-19 |
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| CN111039291A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院金属研究所 | Method for preparing NbC and/or TaC powder in situ by molten salt disproportionation reaction |
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| CN102872903B (en) * | 2012-10-12 | 2014-08-13 | 常州大学 | Preparation method of in-process shape-selective catalyst for para-xylene synthesis |
| CN103721739B (en) * | 2013-12-20 | 2015-08-05 | 常州大学 | A kind of preparation method of micro porous molecular sieve supported magnesium oxide shape-selective catalyst |
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