CN106582787A - Preparation method of titanium oxide modified microporous molecular sieve shape-selective catalyst - Google Patents
Preparation method of titanium oxide modified microporous molecular sieve shape-selective catalyst Download PDFInfo
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- 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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/88—Growth and elimination reactions
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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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- B01J2229/36—Steaming
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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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- 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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Abstract
The invention relates to a preparation method of a titanium oxide modified microporous molecular sieve shape-selective catalyst. According to the method, a microporous molecular sieve ZSM-5 or MCM-22 is taken as a matrix, tetrabutyl titanate is taken as a precursor, absolute ethyl alcohol is taken as a solvent, titanium oxide is supported to the outer surface of the microporous molecular sieve through equivalent-volume impregnation and water-vapor treatment, and titanium oxide in the catalyst accounts for 3%-10% of the total mass of the catalyst. The shape-selective catalyst obtained with the method has good shape-selective catalysis performance on a process of synthesizing p-xylene through alkylation of toluene and dimethyl carbonate.
Description
Technical field
The present invention relates to the preparation field of shape-selective catalyst, more particularly to a kind of to be used for toluene and dimethyl carbonate alkylation
The preparation method of the titanium oxide modified micropore molecular sieve shape-selective catalyst of synthesis xylol process.
Background technology
Xylol is important industrial chemicals, and its traditional synthetic method is mainly obtained by toluene disproportionation procedure,
But as dismutation needs stronger acidic catalyst and higher reaction temperature, therefore catalyst inactivation is very fast.In recent years
Become the focus of research to synthesize xylol by toluene direct alkylation process.
The catalyst commonly used during alkylation of toluene is the micro porous molecular sieves such as ZSM-5 or MCM-22, alkylated reaction
O-, m- isomer to three kinds of dimethylbenzene can be obtained simultaneously, this mainly due to the xylol generated in course of reaction very
Easily there is isomerization reaction and generate o-Dimethylbenzene and meta-xylene in the outer surface in catalyst.Therefore, want to improve alkyl
The selectivity of xylol during change, that is, the Shape-selective of catalyst is improved, just molecular sieve must be modified.Change
The purpose of property mainly has at 2 points：One is the acid bit quantity for reducing catalyst external surface, reduces product xylol in molecular sieve
The isomerization reaction of outer surface；Two is modulation molecular sieve port size, increases the diffusional resistance of o-Dimethylbenzene and meta-xylene.It is logical
Often modified method has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre- carbon distribution and metal oxide modified.The side of siliceous deposits
Although method can effectively improve the Shape-selective of molecular sieve catalyst, due to the work between molecular sieve surface hydroxyl and deposit
Firmly very weak, the deposition for generally requiring 3～4 times can be only achieved preferable effect, therefore operation is comparatively laborious, and energy consumption is higher.In advance
Carbon distribution can also improve the Shape-selective of molecular sieve catalyst, but as the catalyst after regeneration must also carry out pre- product again
Carbon, therefore operation is loaded down with trivial details, and also it is only limitted to laboratory research at present.Molecular sieve appearance is covered using metal oxide modified
Face acidity bit manipulation is very simple, and once can just complete preferable coverage effect, but the method is reducing outer surface acid
Property while can also cause in duct acid reduction, therefore also fail to large-scale use.Patent (CN102513144B) is adopted
The method of complexation dipping prepares metal oxide modified micro porous molecular sieve shape-selective catalyst, although achieve preferable shape-selective effect
Really, but operating process is loaded down with trivial details, process is wayward；Therefore it is in the urgent need to exploitation is a kind of simple to operate, with low cost and select
The high molecular sieve modified method of shape performance is applied in the building-up process of xylol.
Therefore, finding a kind of efficient oxide modifying micro porous molecular sieve shape-selective catalyst preparation method is used for synthesis to two
Toluene process has important using value.
The content of the invention
The technical problem to be solved in the present invention is for shape-selective catalyst during alkylation of toluene synthesis xylol
Preparation manipulation is loaded down with trivial details, the low problem of high cost, catalytic efficiency, there is provided a kind of synthetic method is simple, with low cost, and Shape-selective is high
Shape-selective catalyst preparation method.
The technical solution adopted for the present invention to solve the technical problems is：
(1) butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve is added to it is above-mentioned molten
In liquid, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:1-1:2；Butyl titanate and microporous molecular
The mass ratio of sieve is 1:9-1:32, stir, be stored at room temperature；
(2) material obtained by step (1) is put in two mouthfuls of flasks, and is passed through steam treatment 2-4h at room temperature, then
Be transferred in Muffle furnace, 550 DEG C be warming up to the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, with
After be down to room temperature, that is, obtain needed for titanium oxide modified micropore molecular sieve shape-selective catalyst, in catalyst, the content of titanium oxide is
The 3%～10% of catalyst gross mass.
Used as limitation of the invention, heretofore described micro porous molecular sieve is ZSM-5 or MCM-22.
Catalyst of the present invention can be used for during toluene and dimethyl carbonate alkyl be combined to xylol.
The butyl titanate that the present invention is adopted has larger molecular dimension, and its molecular dimension is significantly greater than micropore point
The port size of son sieve ZSM-5 and MCM-22, therefore, it is modified by dipping as the predecessor of titanium oxide using butyl titanate
Micro porous molecular sieve can be just prevented effectively from conventional oxide modified micropore molecular sieve shape-selective catalyst preparation process to molecular sieve
The problem of duct blocking.Although in dipping process, butyl titanate is mainly scattered in micro porous molecular sieve outer surface, traditional
Preparation method generally requires experience drying and roasting process.Due to only 206 DEG C of butyl titanate boiling point, therefore in drying and roasting
During be easy to cause butyl titanate volatilization and cause the titanium oxide content on catalyst too low.Also result in simultaneously and prepared
The waste of butyl titanate in journey.
The present invention is scattered in micro porous molecular sieve outer surface by infusion process by titania precursor body of butyl titanate,
Then pass through steam treatment to cause the hydrolysis of butyl titanate and produce titanium oxide.So as to avoid in follow-up roasting process
In cause titania precursor logistics lose problem.And the method using steam treatment makes tetrabutyl titanate hydrolysis keep away
The catalyst surface for exempting from titanium oxide is reunited and reduces which and select type performance.Therefore the present invention has preparation method simple, with low cost,
The advantages of Shape-selective is high.
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
Butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
In solution, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:1；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:10, stir, be stored at room temperature；Material obtained by above-mentioned steps is put in two mouthfuls of flasks, and in room temperature
Under be passed through steam treatment 2h, transfer in Muffle furnace, be warming up to 550 DEG C with the speed of 10 DEG C/min in air atmosphere,
And 4h is kept at this temperature, and be subsequently reduced to room temperature, that is, the titanium oxide modified micropore molecular sieve shape-selective catalyst needed for obtaining, note
For CAT1.
Embodiment 2
Butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
In solution, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:2；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:15, stir, be stored at room temperature；Material obtained by above-mentioned steps is put in two mouthfuls of flasks, and in room temperature
Under be passed through steam treatment 2h, transfer in Muffle furnace, be warming up to 550 DEG C with the speed of 10 DEG C/min in air atmosphere,
And 4h is kept at this temperature, and be subsequently reduced to room temperature, that is, the titanium oxide modified micropore molecular sieve shape-selective catalyst needed for obtaining, note
For CAT2.
Embodiment 3
Butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
In solution, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:1.5；Butyl titanate and microporous molecular
The mass ratio of sieve is 1:32, stir, be stored at room temperature；Material obtained by above-mentioned steps is put in two mouthfuls of flasks, and in room
Steam treatment 4h is passed through under temperature, is transferred in Muffle furnace, 550 are warming up to the speed of 10 DEG C/min in air atmosphere
DEG C, and 4h is kept at this temperature, room temperature is subsequently reduced to, that is, the titanium oxide modified micropore molecular sieve shape selective catalysis needed for obtaining
Agent, is designated as CAT3.
Embodiment 4
Butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve MCM-22 is added to it is above-mentioned
In solution, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:1；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:20, stir, be stored at room temperature；Material obtained by above-mentioned steps is put in two mouthfuls of flasks, and in room temperature
Under be passed through steam treatment 4h, transfer in Muffle furnace, be warming up to 550 DEG C with the speed of 10 DEG C/min in air atmosphere,
And 4h is kept at this temperature, and be subsequently reduced to room temperature, that is, the titanium oxide modified micropore molecular sieve shape-selective catalyst needed for obtaining, note
For CAT4.
Embodiment 5
Butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve MCM-22 is added to it is above-mentioned
In solution, stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:2；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:9, stir, be stored at room temperature；Material obtained by above-mentioned steps is put in two mouthfuls of flasks, and at room temperature
Steam treatment 3h is passed through, is transferred in Muffle furnace, 550 DEG C are warming up to the speed of 10 DEG C/min in air atmosphere, and
4h is kept at this temperature, room temperature is subsequently reduced to, that is, the titanium oxide modified micropore molecular sieve shape-selective catalyst needed for obtaining is designated as
CAT5。
The titanium oxide modified micropore molecular sieve for obtaining in above-described embodiment is used for into toluene and dimethyl carbonate alkylation
With into during xylol, type reaction condition is：400 DEG C of reaction temperature, raw materials quality air speed are 0.8h-1, it is continuous to evaluate
8h.The catalytic performance of each catalyst is as shown in table 1：
The catalytic performance of 1 catalyst of table
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| CAT1 | 24.1 | 72.2 |
| CAT2 | 26.0 | 67.1 |
| CAT3 | 32.7 | 56.9 |
| CAT4 | 29.2 | 61.4 |
| CAT5 | 21.5 | 75.2 |
From 1 result of table, the titanium oxide modified micropore molecular sieve catalyst prepared by the present invention is closed to alkylation of toluene
There is good catalytic performance into xylol process, not only realize higher toluene conversion, and have also obtained very well
Shape-selective.
With the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various change and modification can be carried out in the range of without departing from this invention technological thought entirely.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 (3)
1. a kind of preparation method of titanium oxide modified micropore molecular sieve shape-selective catalyst, it is characterised in that the method is according to following
What step was carried out：
(1) butyl titanate is added in dehydrated alcohol, it is to be mixed it is uniform after micro porous molecular sieve is added in above-mentioned solution,
Stir, wherein butyl titanate and the mass ratio of dehydrated alcohol are 1:1-1:2；The matter of butyl titanate and micro porous molecular sieve
Amount is than being 1:9-1:32, stir, be stored at room temperature；
(2) material obtained by step (1) is put in two mouthfuls of flasks, and is passed through steam treatment 2-4h at room temperature, retransferred
Into Muffle furnace, 550 DEG C are warming up to the speed of 10 DEG C/min in air atmosphere, and keep 4h at this temperature, subsequently drop
To room temperature, that is, the titanium oxide modified micropore molecular sieve shape-selective catalyst needed for obtaining, in catalyst, the content of titanium oxide is catalysis
The 3%～10% of agent gross mass.
2. the preparation method of a kind of titanium oxide modified micropore molecular sieve shape-selective catalyst according to claim 1, its feature
It is that wherein described micro porous molecular sieve is ZSM-5 or MCM-22.
3. the preparation method of a kind of titanium oxide modified micropore molecular sieve shape-selective catalyst according to claim 1, its feature
It is that described catalyst can be used for during toluene is combined to xylol with dimethyl carbonate alkyl.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701511A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of fractal structure titanium oxide |
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| CN102872903A (en) * | 2012-10-12 | 2013-01-16 | 常州大学 | Preparation method of in-process shape-selective catalyst for para-xylene synthesis |
| CN104475149A (en) * | 2014-11-13 | 2015-04-01 | 常州大学 | Preparation method of tungsten oxide modified micro-porous molecular sieve shape-selective catalyst |
| CN105198691A (en) * | 2015-09-08 | 2015-12-30 | 山东成泰化工有限公司 | Synthesis method for p-xylene |
-
2016
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| CN101172245A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Methylbenzene shape-selective disproportionation reaction catalyzer |
| CN102872903A (en) * | 2012-10-12 | 2013-01-16 | 常州大学 | Preparation method of in-process shape-selective catalyst for para-xylene synthesis |
| CN104475149A (en) * | 2014-11-13 | 2015-04-01 | 常州大学 | Preparation method of tungsten oxide modified micro-porous molecular sieve shape-selective catalyst |
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| B. XUE ET AL.: "Acid–base properties of TiO2-modified MCM-41 mesoporous silica and its catalytic performance for ortho-selective ethylation of phenol with diethyl carbonate", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701511A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of fractal structure titanium oxide |
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