CN108636444A - A kind of preparation method for dismutation shape-selective catalyst - Google Patents
A kind of preparation method for dismutation shape-selective catalyst Download PDFInfo
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- CN108636444A CN108636444A CN201810378456.XA CN201810378456A CN108636444A CN 108636444 A CN108636444 A CN 108636444A CN 201810378456 A CN201810378456 A CN 201810378456A CN 108636444 A CN108636444 A CN 108636444A
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- shape
- molecular sieve
- dicyanodiamine
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- selective catalyst
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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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- 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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- 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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- 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
- C07C2529/40—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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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- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of preparation methods for dismutation shape-selective catalyst, this method is carrier with micro porous molecular sieve ZSM 5 or MCM 22, the acidic site of micro porous molecular sieve outer surface is covered by alcohol dipping and the method for temperature-programmed calcination using dicyanodiamine as presoma, to improve the Shape-selective of catalyst.The catalyst that the present invention obtains has good shape selective catalysis performance to toluene disproportionation and ethylbenzene disproportionation process, and preparation method is simple, of low cost.
Description
Technical field
The present invention relates to the preparation fields of composite material, more particularly to a kind of preparation for dismutation shape-selective catalyst
Method.
Background technology
The process that toluene disproportionation synthesizes paraxylene is typical shape selective catalysis process.Micro porous molecular sieve ZSM-5 and MCM-
22 be all the common catalyst in shape selective catalysis field.However, since these micro porous molecular sieve outer surfaces are with the presence of a large amount of acidic sites,
This result in the contraposition product generated in micro porous molecular sieve duct be easy to occur on the acidic site of molecular sieve outer surface it is different
Structureization is reacted, to reduce the selectivity of contraposition product.In order to which the highly selective paraxylene that obtains just must be to micropore point
Son sieve is modified to reduce the quantity of its outer surface acidity position.Common method of modifying has chemical gaseous phase siliceous deposits, chemical liquids
Phase siliceous deposits, pre- carbon distribution and metal oxide modified.Although the method for siliceous deposits can effectively improve selecting for molecular sieve catalyst
Shape performance, but since the active force between molecular sieve surface hydroxyl and deposit is very weak, generally require 3~4 deposition ability
Reach preferable effect, therefore operation is comparatively laborious, energy consumption is higher.Pre- carbon distribution can also improve the shape selectivity of molecular sieve catalyst
Can, but since the catalyst after regeneration must also carry out pre- carbon distribution again, operation is loaded down with trivial details, and is also only limitted to reality at present
Test room research.It is very simple come the operation for covering molecular sieve outer surface acidity position using metal oxide modified, and once
It can complete preferably to cover, but this method can also cause reduction acid in duct while reducing outer surface acidity, because
This also fails to large-scale use.
Carbonitride is a kind of new carbon, and carbonitride load and the outer surface of micro porous molecular sieve can effectively be covered it
The acidic site of outer surface.Melamine is a kind of common predecessor for synthesizing carbonitride.Prepare what carbonitride used in the process
Predecessor melamine have larger molecular dimension, therefore in the mixed process with micro porous molecular sieve melamine be cannot
Acidic site in its hole is influenced in into microporous molecular sieve pore, this is highly beneficial to the Acidity in protection molecular sieve pore passage.So
And dissolubility of the melamine in nearly all solvent is all very poor, therefore it is micro- to use the method impregnated to be dispersed in
There are larger difficulty for porous molecular sieve outer surface；Also it has been reported that and is mixed melamine and micro porous molecular sieve using the method for mechanical lapping
It closes, but mechanical lapping can only achieve the micromixing of melamine and micro porous molecular sieve, to the microcosmic of two kinds of materials of realization
It mixes hardly possible.Carbon nitride precursor is covering molecular sieve outer surface acidity position in the evenly dispersed of micro porous molecular sieve surface
Key.Therefore, a kind of dispersing method of the practicable nitridation carbon matrix precursor of searching in micro porous molecular sieve outer surface seems outstanding
It is important.The present invention uses dicyanodiamine to nitrogenize carbon matrix precursor, so that dicyanodiamine is scattered at high temperature using ethyl alcohol as solvent
Micro porous molecular sieve surface can greatly improve dicyanodiamine and micro porous molecular sieve mass ratio, be nitrogenized to improve in final product
The mass content of carbon, this is all highly beneficial to the coverage effect and its Shape-selective of raising micro porous molecular sieve outer surface acidity position
's.
Invention content
The technical problem to be solved by the present invention is to the preparations for shape-selective catalyst during toluene disproportionation and ethylbenzene disproportionation
It is cumbersome, it is of high cost, and Shape-selective is not high the problems such as, it is simple to provide a kind of synthetic method, of low cost, Shape-selective
High shape-selective catalyst preparation method.
The technical solution adopted by the present invention to solve the technical problems is：
A certain amount of dicyanodiamine and absolute ethyl alcohol are mixed, wherein the mass ratio of dicyanodiamine and ethyl alcohol is 1:1-1:5；
Micro porous molecular sieve is add to the above mixed solution, and is heated to 30-50 DEG C；The mixture of gained is put into baking oven
Be evaporated, be subsequently placed into Muffle furnace, 500 DEG C are warming up to the speed of 5~10 DEG C/min, be subsequently reduced to room temperature obtain it is described
Shape-selective catalyst.
As limitation of the invention, micro porous molecular sieve of the present invention is ZSM-5 or MCM-22；The dicyan two
The mass ratio of amine and micro porous molecular sieve is 0.05:1~0.2:1.
Catalyst of the present invention can be applied to toluene disproportionation and ethylbenzene disproportionation process.
The present invention for the first time using dicyanodiamine as presoma by alcohol dipping and the method for temperature-programmed calcination by carbonitride
Material load not only can effectively cover the acidic site of molecular sieve outer surface in micro porous molecular sieve outer surface, but also can protect its hole
Interior acidic site is unaffected, while maintaining higher catalyst activity, the Shape-selective of catalyst is made to further increase.It is logical
Effective covering of outer surface acidity position can be realized by crossing means provided by the invention once, but also can greatly improve dicyan
The mass ratio of diamines and micro porous molecular sieve, to improve the content of carbonitride on micro porous molecular sieve outer surface, this is to fully covering
Its outer surface acidity position is advantageous.Therefore the advantages that present invention has preparation method simple, of low cost, and Shape-selective is high.
Specific implementation mode
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
By dicyanodiamine and absolute ethyl alcohol mix, wherein the mass ratio of dicyanodiamine and ethyl alcohol be 1:5；By microporous molecular
Sieve ZSM-5 is add to the above mixed solution, and the mass ratio of dicyanodiamine and ZSM-5 is made to reach 0.1:1；And it is heated to 30
℃；Then the mixture of gained is put into baking oven and is evaporated, is subsequently moved in Muffle furnace, is warming up to the speed of 10 DEG C/min
It 500 DEG C, is subsequently reduced to room temperature and obtains the shape-selective catalyst, be denoted as CAT-1.
Embodiment 2
By dicyanodiamine and absolute ethyl alcohol mix, wherein the mass ratio of dicyanodiamine and ethyl alcohol be 1:1；By microporous molecular
Sieve ZSM-5 is add to the above mixed solution, and the mass ratio of dicyanodiamine and ZSM-5 is made to reach 0.2:1；And it is heated to 50
℃；Then the mixture of gained is put into baking oven and is evaporated, is subsequently moved in Muffle furnace, 500 are warming up to the speed of 5 DEG C/min
DEG C, it is subsequently reduced to room temperature and obtains the shape-selective catalyst, be denoted as CAT-2.
Embodiment 3
By dicyanodiamine and absolute ethyl alcohol mix, wherein the mass ratio of dicyanodiamine and ethyl alcohol be 1:3；By microporous molecular
Sieve ZSM-5 is add to the above mixed solution, and the mass ratio of dicyanodiamine and ZSM-5 is made to reach 0.05:1；And it is heated to
40℃；Then the mixture of gained is put into baking oven and is evaporated, is subsequently moved in Muffle furnace, is warming up to the speed of 7 DEG C/min
It 500 DEG C, is subsequently reduced to room temperature and obtains the shape-selective catalyst, be denoted as CAT-3.
Embodiment 4
By dicyanodiamine and absolute ethyl alcohol mix, wherein the mass ratio of dicyanodiamine and ethyl alcohol be 1:4；By microporous molecular
Sieve MCM-22 is add to the above mixed solution, and the mass ratio of dicyanodiamine and MCM-22 is made to reach 0.1:1；And it is heated to
30℃；Then the mixture of gained is put into baking oven and is evaporated, is subsequently moved in Muffle furnace, is warming up to the speed of 10 DEG C/min
It 500 DEG C, is subsequently reduced to room temperature and obtains the shape-selective catalyst, be denoted as CAT-4.
Embodiment 5
By dicyanodiamine and absolute ethyl alcohol mix, wherein the mass ratio of dicyanodiamine and ethyl alcohol be 1:3；By microporous molecular
Sieve MCM-22 is add to the above mixed solution, and the mass ratio of dicyanodiamine and MCM-22 is made to reach 0.2:1；And it is heated to
50℃；Then the mixture of gained is put into baking oven and is evaporated, is subsequently moved in Muffle furnace, is warming up to the speed of 5 DEG C/min
It 500 DEG C, is subsequently reduced to room temperature and obtains the shape-selective catalyst, be denoted as CAT-5.
During obtained catalyst in above-described embodiment is used for toluene disproportionation and ethylbenzene disproportionation, typical reaction condition
For：500 DEG C of reaction temperature, material quality air speed are 1h-1, continuously evaluate 6h.The catalytic performance of each catalyst is as shown in table 1：
Catalytic performance of 1 catalyst of table to toluene disproportionation procedure
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| CAT1 | 40.3 | 70.5 |
| CAT2 | 34.1 | 84.2 |
| CAT3 | 42.9 | 67.4 |
| CAT4 | 37.5 | 78.1 |
| CAT5 | 30.7 | 87.6 |
Catalytic performance of 2 catalyst of table to ethylbenzene disproportionation process
| Catalyst | Conversion of ethylbenzene (%) | P-Diethylbenzene selectivity (%) |
| CAT1 | 43.3 | 82.9 |
| CAT2 | 39.5 | 92.6 |
| CAT3 | 45.6 | 77.5 |
| CAT4 | 41.0 | 88.2 |
| CAT5 | 35.8 | 95.7 |
By Tables 1 and 2 result as it can be seen that the having very to toluene disproportionation and ethylbenzene disproportionation process of the catalyst prepared by the present invention
Good catalytic performance, not only realizes higher toluene conversion, but also have also obtained good Shape-selective.
It is enlightenment with above-mentioned desirable embodiment according to the present invention, 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 determine its technical scope according to right.
Claims (4)
1. a kind of preparation method for dismutation shape-selective catalyst, it is characterised in that this method is to carry out as steps described below
's：
(1) a certain amount of dicyanodiamine and absolute ethyl alcohol are mixed, wherein the mass ratio of dicyanodiamine and ethyl alcohol is 1:1-1:5；
(2) micro porous molecular sieve is added in mixed solution obtained by step (1), and is heated to 30-50 DEG C；
(3) mixture obtained by step (2) is put into baking oven and is evaporated, is subsequently placed into Muffle furnace, with the speed of 5~10 DEG C/min
Degree is warming up to 500 DEG C, is subsequently reduced to room temperature and obtains the shape-selective catalyst.
2. a kind of preparation method for dismutation shape-selective catalyst according to claim 1, it is characterised in that described
Micro porous molecular sieve be ZSM-5 or MCM-22.
3. a kind of preparation method for dismutation shape-selective catalyst according to claim 1, it is characterised in that described
Dicyanodiamine and micro porous molecular sieve mass ratio be 0.05:1~0.2:1.
4. a kind of preparation method for dismutation shape-selective catalyst according to claim 1, it is characterised in that described
Shape-selective catalyst can be applied to toluene disproportionation and ethylbenzene disproportionation process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569718A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method of melem modified micropore molecular sieve shape-selective catalyst |
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| CN102872904A (en) * | 2012-10-12 | 2013-01-16 | 常州大学 | Method for preparing shape-selective catalyst |
| CN103381371A (en) * | 2013-07-16 | 2013-11-06 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN103664477A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Toluene shape-selective disproportionation method |
| CN106563492A (en) * | 2016-11-10 | 2017-04-19 | 常州大学 | Preparation method for titanium oxide modified microporous molecular sieve shape-selective catalyst |
| 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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2018
- 2018-04-25 CN CN201810378456.XA patent/CN108636444A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664477A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Toluene shape-selective disproportionation method |
| CN102872904A (en) * | 2012-10-12 | 2013-01-16 | 常州大学 | Method for preparing shape-selective catalyst |
| CN103381371A (en) * | 2013-07-16 | 2013-11-06 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN106563492A (en) * | 2016-11-10 | 2017-04-19 | 常州大学 | Preparation method for titanium oxide modified microporous molecular sieve shape-selective catalyst |
| CN106582786A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Preparation method of boron modification microporous molecular sieve shape-selective catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109569718A (en) * | 2018-12-05 | 2019-04-05 | 常州大学 | A kind of preparation method of melem modified micropore molecular sieve shape-selective catalyst |
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Application publication date: 20181012 |