CN104492478A - Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst - Google Patents
Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst Download PDFInfo
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- CN104492478A CN104492478A CN201410673757.7A CN201410673757A CN104492478A CN 104492478 A CN104492478 A CN 104492478A CN 201410673757 A CN201410673757 A CN 201410673757A CN 104492478 A CN104492478 A CN 104492478A
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Abstract
The invention relates to a preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst. The method uses a microporous molecular sieve ZSM-5 or MCM-22 as a matrix, phosphoric acid as a precursor and ethanol as a solvent, and employs an impregnating method to load phosphorus oxide on the microporous molecular sieve, wherein the content of phosphorus oxide in the catalyst accounts for 5%-10% of the total weight of the catalyst. The shape-selective catalyst obtained by the invention has good shape-selective catalysis performance on the synthesis of p-diethyl benzene by styralyl alcohol alkylation.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, particularly a kind of preparation method of the phosphoric acid modification micro porous molecular sieve shape-selective catalyst for ethylbenzene ethanol alkylation synthesis p-Diethylbenzene process.
Background technology
The process of ethylbenzene ethanol alkylation synthesis p-Diethylbenzene is typical shape selective catalysis process.Micro porous molecular sieve such as ZSM-5 and MCM-22 is the shape-selective catalyst that this process is commonly used.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 p-Diethylbenzene generated in molecular sieve pore passage in ethylbenzene alkylation process, thus reduces the selective of contraposition product.Obtaining p-Diethylbenzene 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 micro porous molecular sieve outer surface acidity position very simply, and once just can complete good covering.Be that to prepare oxide modifying micro porous molecular sieve shape-selective catalyst be exactly conventional method of modifying to phosphorous oxide predecessor with phosphoric acid.Conventional oxidation P Modification micro porous molecular sieve shape-selective catalyst often adopts water to be solvent, 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 ethylbenzene alkylation process.Also the report (103406142A) phosphate being used for modified micropore molecular sieve phosphorous oxide modified micropore molecular sieve catalyst is had.Although phosphate avoids more greatly the blocking to micro porous molecular sieve duct in dipping process due to molecular dimension, there is Evaporation Phenomenon in phosphate, cause phosphorous oxide load capacity accurately to calculate in oven dry and roasting process; In addition, compared with phosphoric acid, phosphate is expensive, does not possess industrial applications and is worth.
Therefore, the preparation method finding a kind of efficient oxide modifying micro porous molecular sieve shape-selective catalyst has important using value.
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 ethylbenzene ethanol alkylation synthesis p-Diethylbenzene process, high in cost of production problem, there is provided 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:
Catalyst of the present invention is matrix with micro porous molecular sieve, is presoma with phosphoric acid, and to take ethanol as solvent by infusion process be carried on phosphorous oxide, and micro porous molecular sieve obtains.
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve and absolute ethyl alcohol is 1:2-1:4, and the mass ratio of micro porous molecular sieve and phosphoric acid is 100:7-100:15; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 500-600 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst.
As limitation of the invention, described micro porous molecular sieve is ZSM-5 or MCM-22, and in described phosphoric acid modification micro porous molecular sieve shape-selective catalyst, the load capacity of phosphorous oxide is 5% ~ 10% of catalyst gross mass,
In addition, P of the present invention
2o
5modified micropore molecular sieve shape-selective catalyst can be applied to ethylbenzene ethanol alkylation synthesis p-Diethylbenzene process.
The present invention adopts phosphoric acid to be phosphorous oxide predecessor, take ethanol as solvent, infusion process is adopted to carry out modification to micro porous molecular sieve ZSM-5 and MCM-22 molecular sieve, compared with the phosphoric acid modification microporous molecular sieve catalyst prepared with water as solvent, the catalytic activity of molecular sieve in alkylation process is effectively retained, selective, significantly improve, its reason may be have good inhibitory action owing to diffusing in molecular sieve pore passage for phosphoric acid during employing ethanol as solvent, thus controls part phosphoric acid at molecular sieve outer surface.So just make both to reduce inner acidic position, micro porous molecular sieve duct to be covered by phosphoric acid, cause the minimizing of acidic site quantity on catalyst and the diffusion difficulty of course of reaction Raw and product, but also the effective coverage of phosphorous oxide to micro porous molecular sieve outer surface acidity position can be increased, thus suppress the generation of p-Diethylbenzene isomerization reaction on molecular sieve outer surface acidity position.Adopting ethanol as solvent to prepare this beneficial effect of phosphoric acid modification micro porous molecular sieve shape-selective catalyst should owing to the stronger hydrogen bond action in dipping process between ethanol and phosphoric acid molecules, make phosphoric acid molecules in dipping process with the material of larger molecular dimension exist, and with do not have during water as solvent this hydrogen bond or Hyarogen-bonding more weak.Phosphoric acid is the most cheap phosphorous oxide predecessor, and compared with other phosphorous oxide predecessors, as phosphate, its preparation cost is obviously less.
The present invention is that phosphoric acid modification microporous molecular sieve catalyst prepared by solvent first with ethanol, both the acidic site of molecular sieve outer surface can have been covered, again can the capped degree of reduce orifice inner acidic position, while maintaining higher catalyst activity, the Shape-selective of catalyst is improved.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
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve ZSM-5 and absolute ethyl alcohol is 1:2, and the mass ratio of micro porous molecular sieve ZSM-5 and phosphoric acid is 100:7; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 500 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-1.
Embodiment 2
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve ZSM-5 and absolute ethyl alcohol is the mass ratio of 1:2 micro porous molecular sieve ZSM-5 and phosphoric acid is 100:15; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 500 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-2.
Embodiment 3
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve ZSM-5 and absolute ethyl alcohol is the mass ratio of 1:4 micro porous molecular sieve ZSM-5 and phosphoric acid is 100:7; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 600 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-3.
Embodiment 4
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve MCM-22 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve MCM-22 and absolute ethyl alcohol is the mass ratio of 1:4 micro porous molecular sieve MCM-22 and phosphoric acid is 100:15; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-4.
Embodiment 5
Phosphoric acid crystallization is joined in absolute ethyl alcohol, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve ZSM-5 and absolute ethyl alcohol is the mass ratio of 1:4 micro porous molecular sieve ZSM-5 and phosphoric acid is 100:10; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-5.
Comparative example
Phosphoric acid crystallization is added in deionized water, is stirred to and mixes; Added in above-mentioned solution by micro porous molecular sieve ZSM-5 subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve ZSM-5 and deionized water is the mass ratio of 1:4 micro porous molecular sieve ZSM-5 and phosphoric acid is 100:10; By the material of above-mentioned steps gained evaporate to dryness in a water bath, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst, be designated as CAT-6.
Be used in ethylbenzene ethanol alkylation process by the phosphoric acid modification micro porous molecular sieve obtained in above-described embodiment, typical reaction condition is: ethylbenzene and ethanol mol ratio are 2:1, reaction temperature 360 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 each embodiment catalyst of table 1
| Catalyst | Conversion of ethylbenzene (%) | P-Diethylbenzene selective (%) |
| CAT-1 | 25.1 | 90.7 |
| CAT-2 | 17.2 | 96.2 |
| CAT-3 | 24.9 | 91.1 |
| CAT-4 | 16.8 | 97.4 |
| CAT-5 | 21.3 | 95.5 |
| CAT-6 | 13.0 | 96.2 |
From table 1 result, the phosphoric acid modification microporous molecular sieve catalyst prepared by the present invention has good catalytic performance to ethylbenzene ethanol alkylation process, not only achieves higher conversion of ethylbenzene, but also obtains good Shape-selective.Be compared with the phosphoric acid modification microporous molecular sieve catalyst (CAT-6 of the product that comparative example obtains) prepared of solvent with water with traditional, the catalyst prepared by the present invention shows more excellent catalytic performance.
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 (5)
1. a preparation method for phosphoric acid modification micro porous molecular sieve shape-selective catalyst, it is characterized in that this catalyst is is matrix with micro porous molecular sieve, is presoma with phosphoric acid, and to take ethanol as solvent by infusion process be carried on phosphorous oxide, and micro porous molecular sieve obtains.
2. the preparation method of a kind of phosphoric acid modification micro porous molecular sieve shape-selective catalyst according to claim 1, is characterized in that what the method was specifically carried out according to following step:
(1) phosphoric acid crystallization is joined in absolute ethyl alcohol, be stirred to and mix; Added in above-mentioned solution by micro porous molecular sieve subsequently, stir, room temperature leaves standstill; Wherein the mass ratio of micro porous molecular sieve and absolute ethyl alcohol is 1:2-1:4, and the mass ratio of micro porous molecular sieve and phosphoric acid is 100:7-100:15;
(2) by the material evaporate to dryness in a water bath of step (1) gained, put into baking oven subsequently dry, transfer in Muffle furnace, in air atmosphere, be warming up to 500-600 DEG C, be down to room temperature subsequently, namely obtain required phosphoric acid modification micro porous molecular sieve shape-selective catalyst.
3. the preparation method of a kind of phosphoric acid modification micro porous molecular sieve shape-selective catalyst according to claim 1 and 2, is characterized in that wherein said micro porous molecular sieve is ZSM-5 or MCM-22.
4. the preparation method of a kind of phosphoric acid modification micro porous molecular sieve shape-selective catalyst according to claim 1 and 2, is characterized in that the load capacity of phosphorous oxide in described phosphoric acid modification micro porous molecular sieve shape-selective catalyst is 5% ~ 10% of catalyst gross mass.
5. the preparation method of a kind of phosphoric acid modification micro porous molecular sieve shape-selective catalyst according to claim 1 and 2, is characterized in that described catalyst can be used in ethylbenzene ethanol alkylation synthesis p-Diethylbenzene process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582786A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Preparation method of boron modification microporous molecular sieve shape-selective catalyst |
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| US20120157741A1 (en) * | 2010-12-17 | 2012-06-21 | Guang Cao | Synthesis of Silicoaluminophosphate Having Lev Framework-Type |
| CN103406142A (en) * | 2013-07-16 | 2013-11-27 | 常州大学 | Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst |
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Patent Citations (3)
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| CN1422694A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Catalyst for reduction of nitrogen oxide, its preparation method and use |
| US20120157741A1 (en) * | 2010-12-17 | 2012-06-21 | Guang Cao | Synthesis of Silicoaluminophosphate Having Lev Framework-Type |
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| CN106582786A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Preparation method of boron modification microporous molecular sieve shape-selective catalyst |
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