CN109569702A - A kind of preparation method and application of carbonitride modified micropore molecular sieve shape-selective catalyst - Google Patents
A kind of preparation method and application of carbonitride modified micropore molecular sieve shape-selective catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of preparation method and application of carbonitride modified micropore molecular sieve shape-selective catalyst, this method disperses carbonitride in by the method for ultrasonic disperse the outer surface of micro porous molecular sieve using micro porous molecular sieve MCM-22 and ZSM-5 as matrix.The shape-selective catalyst that the present invention obtains has good shape selective catalysis performance to toluene disproportionation synthesis paraxylene process.
Description
Technical field
The present invention relates to the preparation fields of shape-selective catalyst, in particular to a kind of to synthesize paraxylene mistake for toluene disproportionation
The preparation method of the modified micropore molecular sieve shape-selective catalyst of journey.
Background technique
Paraxylene is important industrial chemicals, and traditional synthetic method is mainly obtained by toluene disproportionation procedure.
Common catalyst is that micro porous molecular sieves, the alkylated reactions such as ZSM-5 or MCM-22 can obtain simultaneously in toluene disproportionation procedure
Isomers o-, m-, to three kinds of dimethylbenzene, this is mainly due to the paraxylene generated in reaction process to be easy in catalyst
Outer surface occur isomerization reaction and generate ortho-xylene and meta-xylene.Therefore, to improve dismutation in diformazan
The selectivity of benzene, that is, the Shape-selective of catalyst is improved, molecular sieve must be just modified.Modified purpose mainly has
Two o'clock: first is that reducing the acid bit quantity of catalyst external surface, product paraxylene is reduced in the isomerization of molecular sieve outer surface
Reaction；Second is that modulation molecular sieve port size, increases the diffusional resistance of ortho-xylene and meta-xylene.
There are chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre- carbon distribution and metal oxygen to molecular sieve modified method at present
Compound is modified.Although the method for siliceous deposits can effectively improve the Shape-selective of molecular sieve catalyst, but due to molecular sieve surface
Active force between hydroxyl and deposit is very weak, and generally requiring 3~4 depositions can be only achieved preferable effect, therefore operate
Comparatively laborious, energy consumption is higher.Pre- carbon distribution can also be improved the Shape-selective of molecular sieve catalyst, but due to the catalysis after regeneration
Agent must also carry out pre- carbon distribution again, therefore operation is loaded down with trivial details, and also be only limitted to laboratory research at present.Using metal oxide
Modification is very simple to cover molecular sieve outer surface acidity bit manipulation, and can once complete preferable coverage effect, but
This method can also cause reduction acid in duct while reducing outer surface acidity, therefore also fail to large-scale use.
Therefore a kind of efficient modified micropore molecular sieve shape-selective catalyst preparation method is found for synthesizing paraxylene mistake
Journey has important application value.
Summary of the invention
The technical problem to be solved by the present invention is to the systems for shape-selective catalyst during toluene disproportionation synthesis paraxylene
It is standby cumbersome, it is at high cost, catalytic efficiency is low the problems such as, it is simple to provide a kind of preparation method, low in cost, in toluene synthesis pair
The high shape-selective catalyst preparation method of Shape-selective during dimethylbenzene.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of carbonitride modified micropore molecular sieve shape-selective catalyst, it is characterised in that this method is under
State step progress:
(1) micro porous molecular sieve is add to deionized water, room temperature ultrasonic disperse 30min, wherein micro porous molecular sieve with go
The mass ratio of ionized water is 1:20-1:50；
(2) into step (1) resulting mixture, it is gradually added nitridation carbon dust, each additional amount is micropore in solution
The 1-2% of molecular sieve quality is ultrasonically treated 30min after being added every time, adds 5-10 times altogether；
(3) the resulting mixture of step (1) is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and
2h is kept at a temperature of this, is subsequently reduced to room temperature to get required carbonitride modified micropore molecular sieve shape-selective catalyst is arrived.
Wherein the carbonitride the preparation method is as follows:
6g melamine (Melamine) is taken to be placed in crucible with cover, then with 3 DEG C of min in Muffle furnace-1Liter
Warm rate is heated to 550 DEG C and keeps 3h, and obtaining 2g or so faint yellow solid is carbon nitride material.
As limitation of the invention, micro porous molecular sieve of the present invention is ZSM-5 or MCM-22.
Catalyst of the present invention can be used for during toluene disproportionation synthesis paraxylene, have to product paraxylene
High selectivity.
MCM-22 of the present invention the preparation method is as follows:
13.3g sodium hydroxide is dissolved in 443mL deionized water；Then to addition 4g NaAlO in above-mentioned solution2With
38ml hexamethylene imine, and be vigorously stirred；195mL silica solution is slowly dropped to above-mentioned solution under vigorous stirring, is continued
Strong stirring 30min.Gained white gels are moved into the crystallizing kettle of polytetrafluoroethyllining lining, in 150 DEG C of baking oven crystallization 7 days；
Then filter, washing to pH=8.0,110 DEG C of drying for 24 hours, then in Muffle furnace 550 DEG C of roasting 8h up to micro porous molecular sieve
MCM-22。
ZSM-5 of the present invention the preparation method is as follows:
First 12.5g sodium hydroxide is dissolved in 288mL deionized water；Then to the NaAlO that 3.7g is added in solution2With
195mL tetrapropylammonium hydroxide solution, and be vigorously stirred；The silica gel solution of 195mL is slowly dropped under vigorous stirring molten
In liquid, continue strong stirring 30min.Then white gels are moved into the crystallizing kettle of polytetrafluoroethyllining lining, at 160 DEG C of baking oven
Crystallization 3 days；Filtering, washing to pH=9.0,110 DEG C of drying for 24 hours, then in Muffle furnace 550 DEG C of roasting 8h up to microporous molecular
Sieve ZSM-5.
In order to improve micro porous molecular sieve in the Shape-selective of paraxylene synthesis process, to micro porous molecular sieve outer surface acidity
The covering of position is crucial.The method of conventional covering micro porous molecular sieve outer surface acidity position mostly uses SiO2, the substances such as MgO.This
Substance micro porous molecular sieve outer surface dispersion mainly based on Van der Waals force, therefore adsorb insecure, dispersion is uneven, meeting
Reduce the stability and Shape-selective of catalyst.
The present invention can effectively solve the above problems using carbonitride as adsorbate.Carbonitride is that a kind of molecular dimension is larger
Material, structure is as follows:
Carbonitride is a kind of biggish alkaline matter of molecular dimension, and preparation process uses the mode of ultrasonic disperse not only can be with
Layered nitride carbon is effectively peeled off, and carbonitride can be enhanced in the dispersing uniformity of micro porous molecular sieve outer surface.In addition,
Due to nitrogenizing the alkalinity of carbon molecules, make the acidic site of itself and the outer surface micro porous molecular sieve MCM-22 and ZSM-5 that acid-base reaction occur
And firmly it is adsorbed in molecular sieve outer surface.It is excellent steady to make modified molecular sieve catalyst show in toluene disproportionation procedure
Qualitative and Shape-selective.
Detailed description of the invention
Fig. 1 is the XPS characterization result figure of MCM-22 molecular sieve and Cat 1, Cat 2, and wherein A is MCM-22 molecular sieve
XPS characterization result, B are the XPS characterization result of Cat 1, and C is the XPS characterization result of Cat 2, wherein (1) is oxygen (O) element
Characteristic peak, (2) are the characteristic peak of nitrogen (N), and (3) are the characteristic peak of carbon (C) element；
Fig. 2 is the XRD characterization of MCM-22 molecular sieve and Cat 1, Cat 2 as a result, wherein A is the XRD of MCM-22 molecular sieve
Map, B are the XRD spectrum of Cat 1；C is the XRD spectrum of Cat 2；
As seen from Figure 1, N and C element is not detected in MCM-22 molecular sieve surface, and have on Cat1 and Cat2 apparent N,
C element exists, this illustrates that method of the invention can make carbonitride immobilized in the surface MCM-22 well.
From Figure 2 it can be seen that there is no significantly changing for the characteristic diffraction peak of MCM-22 molecular sieve after load carbon nitride material.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1
2g micro porous molecular sieve MCM-22 is added in 40mL deionized water, room temperature ultrasonic disperse 30min；To above-mentioned mixing
In object, it is gradually added nitridation carbon dust, each additional amount is 0.02g, and continuous addition 5 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat1.
Embodiment 2
2g micro porous molecular sieve MCM-22 is added in 100mL deionized water, room temperature ultrasonic disperse 30min；It is mixed to above-mentioned
It closes in object, is gradually added nitridation carbon dust, each additional amount is 0.02g, and continuous addition 10 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat2.
Embodiment 3
2g micro porous molecular sieve MCM-22 is added in 60mL deionized water, room temperature ultrasonic disperse 30min；To above-mentioned mixing
In object, it is gradually added nitridation carbon dust, each additional amount is 0.02g, and continuous addition 7 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat3.
Embodiment 4
2g micro porous molecular sieve ZSM-5 is added in 40mL deionized water, room temperature ultrasonic disperse 30min；To above-mentioned mixing
In object, it is gradually added nitridation carbon dust, each additional amount is 0.02g, and continuous addition 10 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat4.
Embodiment 5
2g micro porous molecular sieve ZSM-5 is added in 50mL deionized water, room temperature ultrasonic disperse 30min；To above-mentioned mixing
In object, it is gradually added nitridation carbon dust, each additional amount is 0.04g, and continuous addition 6 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat5.
Embodiment 6
2g micro porous molecular sieve ZSM-5 is added in 70mL deionized water, room temperature ultrasonic disperse 30min；To above-mentioned mixing
In object, it is gradually added nitridation carbon dust, each additional amount is 0.02g, and continuous addition 9 times is ultrasonically treated after being added every time
30min；Then resulting mixture is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and at this temperature
2h is kept, room temperature is subsequently reduced to get to required carbonitride modified micropore molecular sieve shape-selective catalyst, is denoted as Cat6.
Obtained carbonitride modified micropore molecular sieve in above-described embodiment is used for toluene disproportionation synthesis paraxylene mistake
Cheng Zhong, typical reaction condition are as follows: 400 DEG C of reaction temperature, catalyst amount 2g, toluene flow velocity 5mL/h are continuously evaluated 8h.Respectively urge
The catalytic performance of agent is as shown in table 1:
The catalytic performance of 1 catalyst of table
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| ZSM-5 | 37.5 | 22.1 |
| MCM-22 | 35.9 | 23.5 |
| Cat 1 | 27.4 | 71.6 |
| Cat 2 | 20.5 | 80.7 |
| Cat 3 | 23.1 | 74.9 |
| Cat 4 | 22.6 | 78.1 |
| Cat 5 | 24.9 | 76.5 |
| Cat 6 | 21.5 | 79.2 |
As 1 result of table as it can be seen that oxide modifying microporous molecular sieve catalyst prepared by the present invention closes alkylation of toluene
There is good catalytic performance at paraxylene process, not only realize higher toluene conversion, but also has also obtained very well
Shape-selective.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (4)
1. a kind of preparation method of carbonitride modified micropore molecular sieve shape-selective catalyst, it is characterised in that this method is according to following
What step carried out:
(1) micro porous molecular sieve is add to deionized water, room temperature ultrasonic disperse 30min, wherein micro porous molecular sieve and deionization
The mass ratio of water is 1:20-1:50；
(2) into step (1) resulting mixture, it is gradually added nitridation carbon dust, each additional amount is microporous molecular in solution
The 1-2% of quality is sieved, is ultrasonically treated 30min after being added every time, is added 5-10 times altogether；
(3) the resulting mixture of step (2) is filtered, filter cake is dried into 12h at 80 DEG C, then be warming up to 120 DEG C, and is warm herein
Degree is lower to keep 2h, is subsequently reduced to room temperature to get required carbonitride modified micropore molecular sieve shape-selective catalyst is arrived.
2. a kind of preparation method of carbonitride modified micropore molecular sieve shape-selective catalyst according to claim 1, feature
It is that the wherein described carbonitride is prepared by the following method:
A certain amount of melamine is placed in crucible with cover, with 3 DEG C of min in Muffle furnace-1Heating rate be heated to 550
DEG C and keep 3h, obtaining faint yellow solid is carbon nitride material.
3. a kind of preparation method of carbonitride modified micropore molecular sieve shape-selective catalyst according to claim 1, feature
It is that the wherein described micro porous molecular sieve is ZSM-5 or MCM-22.
4. a kind of application of carbonitride modified micropore molecular sieve shape-selective catalyst according to claim 1, it is characterised in that
The catalyst can be applied to during toluene disproportionation synthesis paraxylene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468166A (en) * | 2020-05-26 | 2020-07-31 | 南华大学 | P modified g-C3N4Preparation method and application of catalyst |
| CN115400786A (en) * | 2022-10-09 | 2022-11-29 | 常州大学 | Surface modification method of microporous molecular sieve |
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| CN104084233A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of boron oxide-modified microporous molecular sieve shape-selective catalyst |
| CN104437600A (en) * | 2014-09-29 | 2015-03-25 | 常州大学 | Method for preparing phosphorus oxide modified microporous molecular sieve shape-selective catalyst |
| JP2015192977A (en) * | 2014-03-31 | 2015-11-05 | 独立行政法人国立高等専門学校機構 | Porous functional material, production method of the same and pollutant removal method using the same |
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| CN103381371A (en) * | 2013-07-16 | 2013-11-06 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN103406142A (en) * | 2013-07-16 | 2013-11-27 | 常州大学 | Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst |
| JP2015192977A (en) * | 2014-03-31 | 2015-11-05 | 独立行政法人国立高等専門学校機構 | Porous functional material, production method of the same and pollutant removal method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115400786A (en) * | 2022-10-09 | 2022-11-29 | 常州大学 | Surface modification method of microporous molecular sieve |
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Application publication date: 20190405 |