CN104084233A - Preparation method of boron oxide-modified microporous molecular sieve shape-selective catalyst - Google Patents
Preparation method of boron oxide-modified microporous molecular sieve shape-selective catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a boron oxide-modified microporous molecular sieve shape-selective catalyst. The preparation method comprises the following step of with a microporous molecular sieve ZSM-5 or MCM-22 as a supporter and ammonium pentaborate as a precursor of boron oxide, supporting boron oxide on the outer surface of the microporous molecular sieve by virtue of dipping and temperature programming roasting methods, wherein the mass ratio of ammonium pentaborate to the microporous molecular sieve is (1:2)-(1:8). The catalyst prepared by virtue of the preparation method has good shape selective catalysis performance in processes of compounding p-cresol and paraethyl phenol by virtue of para-phenol alkylation.
Description
Technical field
The present invention relates to the preparation field of solid inorganic composite, particularly a kind of preparation method of the boron oxide modified micropore molecular sieve shape-selective catalyst for the synthetic p-methyl phenol of phenol contraposition alkylation and paraethyl phenol process.
Background technology
To alkylphenol, if p-methyl phenol and paraethyl phenol are important petrochemicals, be widely used in producing the key areas such as phenolic resins, rubber anti-ageing agent, surfactant, but also be the important intermediate of producing spices and agricultural chemicals.The synthetic method of alkylphenol is mainly contained to natural partition method, methylaniline diazotising Hydrolyze method, methylbenzene chlorinolysis and alkylation of phenol method.Wherein first three methods is due to complex process, and the not high reason of production process seriously corroded and product quality is eliminated gradually, and alkylation of phenol method is the focus of studying at present.Micro porous molecular sieve ZSM-5 and MCM-22 are catalyst the most frequently used in alkylation of phenol process.But, in alkylation of phenol process, alkylphenol is easy to occur isomerization reaction reduces the selective of its contraposition product due to what the existence of molecular sieve outer surface acidity position often caused generating in molecular sieve pore passage.For high selectivity obtain just must carry out modification to reduce the quantity of its outer surface acidity position to micro porous molecular sieve to alkylphenol.Common method of modifying has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre-carbon distribution and oxide modifying.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 good effect, 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 good covering.It is predecessor that but traditional oxide modifying often adopts metal nitrate, phosphoric acid, ammonium dihydrogen phosphate (ADP), boric acid etc., in dipping process, oxide precursor thing is not only scattered in micro porous molecular sieve outer surface, 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 in reducing molecular sieve outer surface acidity bit quantity, also can cause the remarkable decline of catalyst activity when for shape selective catalysis process in improving catalyst Shape-selective.In addition, for the contraposition alkylation process of phenol, conventional metal oxide modified micro porous molecular sieve can not obtain desirable para-selectivity, although reason is that the Bronsted acidic site quantity of molecular sieve outer surface obviously reduces after these oxide modifyings, but can produce a large amount of Lewis acidic sites, and Lewis acidic site is the activated centre of phenol ortho alkylation reaction.
Also there is the preparation (CN103394365A) of the predecessor of researcher using borate as boron oxide for boron oxide modified micropore molecular sieve shape-selective catalyst.The method adopts the larger borate of molecular dimension, and as triethyl borate, triproylborate or butyl borate, for the predecessor of boron oxide is prepared boron oxide modified micropore molecular sieve shape-selective catalyst.Although having overcome tradition, this method prepares the problem of boron oxide modified micropore molecular sieve shape selective catalysis agent method (predecessor taking boric acid as boron oxide) (causing the oxidized boron in molecule sieve aperture inner acidic position to cover), but also there are some problems: if borate is to water sensitive, in preparation process, meeting water can decompose, thereby causes molecular sieve pore passage to be blocked; Again for example, in drying course, easily cause the volatilization of part of boron acid esters and cannot accurately estimate the problems such as actual phosphorous oxides load capacity.
Therefore, find a kind of for the synthetic oxide modifying microporous molecular sieve catalyst that alkylphenol process is had to a high selectivity of phenol contraposition alkylation highly significant.
Summary of the invention
The technical problem to be solved in the present invention is synthetic loaded down with trivial details to the preparation manipulation of shape-selective catalyst in alkylphenol process for alkylation of phenol, and high in cost of production problem, 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:
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:5-1:10, is stirred to completely and dissolves; Micro porous molecular sieve is added in above-mentioned solution subsequently, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve is 1:2-1:8, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, and be down to subsequently room temperature, obtain boron oxide 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;
Phosphorous oxides modified micropore molecular sieve shape-selective catalyst of the present invention can be applied to the synthetic course of reaction to alkylphenol of phenol contraposition alkylation.
The boron oxide predecessor that the present invention adopts is ammonium pentaborate, has larger molecular dimension, is shown below:
The molecular dimension of this material is obviously greater than the port size of micro porous molecular sieve, therefore, adopt this material just can effectively avoid the problem of tradition taking boric acid as boron oxide predecessor modified micropore molecular sieve shape-selective catalyst preparation process as the predecessor of boron oxide by dipping modified micropore molecular sieve.In dipping process, above-mentioned ammonium pentaborate can only be scattered in micro porous molecular sieve outer surface; therefore the boron oxide generating after roasting also can only be 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 molecule sieve aperture inner acidic position.In shape selective catalysis process, not only can significantly improve the Shape-selective of catalyst, and can keep the activity that catalyst is higher.Compared with the boron oxide modified micropore molecular sieve shape-selective catalyst of preparing as the predecessor of boron oxide with borate, method more convenient operation proposed by the invention, preparation condition is required to milder, and especially not high to environment steam content requirement, this amplifies for industrialization is all very favorable.
The present invention is carried on micro porous molecular sieve outer surface by the method for dipping and temperature-programmed calcination by boron oxide taking ammonium pentaborate as boron oxide presoma first; both can effectively cover the acidic site of molecular sieve outer surface; can protect again its inner acidic position, hole unaffected; in maintaining higher catalyst activity, the Shape-selective of catalyst is significantly improved.Therefore to have preparation method simple, with low cost in the present invention, Shape-selective advantages of higher.
Detailed description of the invention
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
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:5, is stirred to completely and dissolves; Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve ZSM-5 is 1:2, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat1.
Embodiment 2
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:10, is stirred to completely and dissolves; Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve ZSM-5 is 1:2, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat2.
Embodiment 3
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:5, is stirred to completely and dissolves; Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve ZSM-5 is 1:8, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat3.
Embodiment 4
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:5, is stirred to completely and dissolves; Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve ZSM-5 is 1:5, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat4.
Embodiment 5
Ammonium pentaborate is added in deionized water, and wherein the mass ratio of ammonium pentaborate and deionized water is 1:5, is stirred to completely and dissolves; Subsequently micro porous molecular sieve MCM-22 is added in above-mentioned solution, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve ZSM-5 is 1:5, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat5.
Comparative example
Boric acid is added in deionized water, and the mass ratio of its mesoboric acid and deionized water is 1:5, is stirred to completely and dissolves; Subsequently micro porous molecular sieve ZSM-5 is added in above-mentioned solution, the mass ratio of its mesoboric acid and micro porous molecular sieve ZSM-5 is 1:5, stirs, and room temperature leaves standstill 12h; By the material of gained evaporate to dryness in water-bath, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst, be designated as Cat6.
The boron oxide modified micropore molecular sieve shape-selective catalyst obtaining in above-described embodiment is respectively used to the alkylation process of phenol and methyl alcohol and the alkylation process of phenol and ethanol, typical reaction condition is: 320 DEG C of reaction temperatures, the mol ratio of phenol and alcohol (methyl alcohol or ethanol) is 1:1, and material quality air speed is 1h
-1, evaluate continuously 6h.The catalytic performance of each catalyst is as shown in Table 1 and Table 2:
The catalytic performance of table 1 catalyst Pyrogentisinic Acid and methyl alcohol contraposition alkylation process
| Catalyst | Phenol conversion (%) | P-methyl phenol selective (%) |
| Cat1 | 40.1 | 72.9 |
| Cat2 | 41.4 | 73.6 |
| Cat3 | 50.8 | 52.4 |
| Cat4 | 45.2 | 59.9 |
| Cat5 | 47.3 | 64.5 |
| Cat6 | 8.4 | 40.7 |
The catalytic performance of table 2 catalyst Pyrogentisinic Acid and ethanol contraposition alkylation process
| Catalyst | Phenol conversion (%) | Paraethyl phenol selective (%) |
| Cat1 | 42.2 | 75.6 |
| Cat2 | 43.6 | 76.1 |
| Cat3 | 52.7 | 57.7 |
| Cat4 | 46.1 | 63.8 |
| Cat5 | 50.0 | 67.6 |
| Cat6 | 10.1 | 44.6 |
As can be seen from Table 1 and Table 2: the boron oxide modified micropore molecular sieve shape-selective catalyst Pyrogentisinic Acid that the present invention is prepared and the contraposition alkylation process of methyl alcohol and phenol and ethanol have good Shape-selective, in keeping higher phenol conversion, can also significantly improve selective to alkylphenol.With traditional taking boric acid as B
2o
3the B of predecessor
2o
3modified micropore molecular sieve catalyst is compared, and the boron oxide modified micropore molecular sieve catalyst Pyrogentisinic Acid contraposition alkylation process of preparing taking ammonium pentaborate as boron oxide predecessor shows more excellent catalytic performance.
Taking above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, relevant staff can, not departing from the scope of this invention technological thought, 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 claim scope.
Claims (3)
1. a preparation method for boron oxide modified micropore molecular sieve shape-selective catalyst, is characterized in that the method carries out according to following step:
(1) ammonium pentaborate is added in deionized water, wherein the mass ratio of ammonium pentaborate and deionized water is 1:5-1:10, is stirred to completely and dissolves; Micro porous molecular sieve is added in above-mentioned solution subsequently, wherein the mass ratio of ammonium pentaborate and micro porous molecular sieve is 1:2-1:8, stirs, and room temperature leaves standstill 12h;
(2) by material evaporate to dryness in water-bath of step (1) gained, put into subsequently the dry 6h of 120 DEG C of baking ovens, transfer in Muffle furnace, in air atmosphere, be warming up to 550 DEG C with the speed of 10 DEG C/min, and keep 4h at this temperature, be down to subsequently room temperature, obtain boron oxide modified micropore molecular sieve shape-selective catalyst.
2. the preparation method of a kind of boron oxide modified micropore molecular sieve shape-selective catalyst according to claim 1, is characterized in that wherein said micro porous molecular sieve is ZSM-5 or MCM-22.
3. the preparation method of a kind of boron oxide modified micropore molecular sieve shape-selective catalyst according to claim 1, is characterized in that this catalyst is applicable to the synthetic course of reaction to alkylphenol of phenol contraposition alkylation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104399514A (en) * | 2014-11-13 | 2015-03-11 | 常州大学 | Preparation method for boric-acid-modified microporous molecular sieve shape-selective catalyst |
| WO2016099781A1 (en) * | 2014-12-15 | 2016-06-23 | Exxonmobil Research And Engineering Company | Boron-selectivated molecular sieves and their use in sorptive separations |
| 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 |
| CN112250081A (en) * | 2020-10-10 | 2021-01-22 | 中北大学 | Preparation method and application of boron oxide quantum dots |
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| CN1605390A (en) * | 2004-09-03 | 2005-04-13 | 南开大学 | Catalyst for synthesizing para diethyl benzene by ethanol and ethyl benzene combination reaction and its preparation method |
| CN103394365A (en) * | 2013-07-16 | 2013-11-20 | 常州大学 | Preparation method of catalyst for phenol para-position alkylation process |
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2014
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| US6090274A (en) * | 1998-12-29 | 2000-07-18 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| CN1605390A (en) * | 2004-09-03 | 2005-04-13 | 南开大学 | Catalyst for synthesizing para diethyl benzene by ethanol and ethyl benzene combination reaction and its preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399514A (en) * | 2014-11-13 | 2015-03-11 | 常州大学 | Preparation method for boric-acid-modified microporous molecular sieve shape-selective catalyst |
| CN104399514B (en) * | 2014-11-13 | 2017-01-18 | 常州大学 | Preparation method for boric-acid-modified microporous molecular sieve shape-selective catalyst |
| WO2016099781A1 (en) * | 2014-12-15 | 2016-06-23 | Exxonmobil Research And Engineering Company | Boron-selectivated molecular sieves and their use in sorptive separations |
| US9597655B2 (en) | 2014-12-15 | 2017-03-21 | Exxonmobil Research And Engineering Company | Boron selectivated molecular sieves and their use in sorptive separations |
| 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 |
| CN112250081A (en) * | 2020-10-10 | 2021-01-22 | 中北大学 | Preparation method and application of boron oxide quantum dots |
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