CN106582787B - A kind of preparation method of titanium oxide modified micropore molecular sieve shape-selective catalyst - Google Patents
A kind of preparation method of titanium oxide modified micropore molecular sieve shape-selective catalyst Download PDFInfo
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- CN106582787B CN106582787B CN201611106137.0A CN201611106137A CN106582787B CN 106582787 B CN106582787 B CN 106582787B CN 201611106137 A CN201611106137 A CN 201611106137A CN 106582787 B CN106582787 B CN 106582787B
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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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- 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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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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 present invention relates to a kind of preparation methods of titanium oxide modified micropore molecular sieve shape-selective catalyst, this method is using micro porous molecular sieve ZSM-5 or MCM-22 as matrix, using butyl titanate as presoma, using dehydrated alcohol as solvent, by the method for incipient impregnation and steam treatment by the content of the titania oxide supported titanium oxide in micro porous molecular sieve outer surface, catalyst be catalyst gross mass 3%~10%.The shape-selective catalyst that the present invention obtains, which is combined to paraxylene process to toluene and dimethyl carbonate alkyl, good shape selective catalysis performance.
Description
Technical field
The present invention relates to the preparation fields of shape-selective catalyst, in particular to a kind of to be alkylated for toluene and dimethyl carbonate
Synthesize the preparation method of the titanium oxide modified micropore molecular sieve shape-selective catalyst of paraxylene process.
Background technique
Paraxylene is important industrial chemicals, and traditional synthetic method is mainly obtained by toluene disproportionation procedure,
But since dismutation needs stronger acidic catalyst and higher reaction temperature, catalyst inactivation very fast.In recent years
It is had become a hot topic of research to synthesize paraxylene by toluene direct alkylation process.
Common catalyst is the micro porous molecular sieves such as ZSM-5 or MCM-22, alkylated reaction during alkylation of toluene
Isomers o-, m-, to three kinds of dimethylbenzene can be obtained simultaneously, and this is mainly due to the paraxylene generated in reaction process very
It is easy to generate ortho-xylene and meta-xylene in the generation isomerization reaction of the outer surface of catalyst.Therefore, to raising alkyl
The selectivity of paraxylene during change, that is, the Shape-selective of catalyst is improved, molecular sieve must be just modified.Change
Property purpose mainly have two o'clock: first is that reduce catalyst external surface acid bit quantity, reduce product paraxylene in molecular sieve
The isomerization reaction of outer surface；Second is that modulation molecular sieve port size, increases the diffusional resistance of ortho-xylene 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, but due to the work between molecular sieve surface hydroxyl and deposit
Firmly very weak, generally requiring 3~4 depositions can be only achieved preferable effect, therefore operation is comparatively laborious, and energy consumption is higher.In advance
Carbon distribution can also be improved the Shape-selective of molecular sieve catalyst, but since the catalyst after regeneration must also carry out pre- product again
Carbon, therefore operation is loaded down with trivial details, and is also only limitted to laboratory research at present.Molecular sieve appearance is covered using metal oxide modified
Face acidity bit manipulation is very simple, and can once complete preferable coverage effect, but this method is reducing outer surface acid
Reduction acid in duct can also be caused while property, therefore also fail to large-scale use.Patent (CN102513144B) uses
The method of complexing dipping prepares metal oxide modified micro porous molecular sieve shape-selective catalyst, although achieving preferable shape-selective effect
Fruit, but operating process is cumbersome, process is not easy to control；Therefore low in cost and select there is an urgent need to develop a kind of easy to operate
The high molecular sieve modified method of shape performance is applied in the synthesis process of paraxylene.
Therefore, a kind of efficient oxide modifying micro porous molecular sieve shape-selective catalyst preparation method is found for synthesizing to two
Toluene process has important application value.
Summary of the invention
The technical problem to be solved by the present invention is to for shape-selective catalyst during alkylation of toluene synthesis paraxylene
The problems such as preparation manipulation is cumbersome, at high cost, catalytic efficiency is low, it is simple to provide a kind of synthetic method, low in cost, and Shape-selective is high
Shape-selective catalyst preparation method.
The technical solution adopted by the present invention to solve the technical problems is:
(1) butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve is added to it is above-mentioned molten
It in liquid, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:1-1:2；Butyl titanate and microporous molecular
The mass ratio of sieve is 1:9-1:32, stirs evenly, is stored at room temperature；
(2) step (1) resulting substance is put into two mouth flask, and is passed through steam treatment 2-4h at room temperature, then
It is transferred in Muffle furnace, is warming up to 550 DEG C in air atmosphere with the speed of 10 DEG C/min, and keep 4h at this temperature, with
It is down to room temperature afterwards to get required titanium oxide modified micropore molecular sieve shape-selective catalyst is arrived, the content of titanium oxide is in catalyst
The 3%~10% of catalyst gross mass.
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 toluene and dimethyl carbonate alkyl is combined to during paraxylene.
The butyl titanate that the present invention uses has biggish molecular dimension, and its molecular dimension is significantly greater than micropore point
The port size of son sieve ZSM-5 and MCM-22, therefore, the predecessor using butyl titanate as titanium oxide is modified by dipping
Micro porous molecular sieve can be avoided effectively in conventional oxide modified micropore molecular sieve shape-selective catalyst preparation process to molecular sieve
The problem of duct blocks.Although butyl titanate is mainly scattered in micro porous molecular sieve outer surface in dipping process, traditional
Preparation method generally requires experience drying and roasting process.Due to only 206 DEG C of butyl titanate boiling point, is drying and roasting
It is easy to that butyl titanate is caused to volatilize and cause the titanium oxide content on catalyst too low in the process.It also results in and prepared simultaneously
The waste of butyl titanate in journey.
The present invention is scattered in micro porous molecular sieve outer surface by infusion process using butyl titanate as titania precursor body,
Steam treatment is then passed through to cause the hydrolysis of butyl titanate and generate titanium oxide.So as to avoid in subsequent roasting process
In cause titania precursor logistics lose the problem of.It and keep away tetrabutyl titanate hydrolysis can also using the method for steam treatment
The catalyst surface for exempting from titanium oxide reunites and reduces it and select type performance.Therefore the present invention has preparation method simple, low in cost,
The advantages that Shape-selective is high.
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
Butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
It in solution, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:1；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:10, stir evenly, be stored at room temperature；The resulting substance of above-mentioned steps is put into two mouth flask, and in room temperature
Under be passed through steam treatment 2h, transfer in Muffle furnace, be warming up to 550 DEG C in air atmosphere with the speed of 10 DEG C/min,
And 4h is kept at this temperature, room temperature is subsequently reduced to get to required titanium oxide modified micropore molecular sieve shape-selective catalyst, is remembered
For CAT1.
Embodiment 2
Butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
It in solution, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:2；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:15, stir evenly, be stored at room temperature；The resulting substance of above-mentioned steps is put into two mouth flask, and in room temperature
Under be passed through steam treatment 2h, transfer in Muffle furnace, be warming up to 550 DEG C in air atmosphere with the speed of 10 DEG C/min,
And 4h is kept at this temperature, room temperature is subsequently reduced to get to required titanium oxide modified micropore molecular sieve shape-selective catalyst, is remembered
For CAT2.
Embodiment 3
Butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve ZSM-5 is added to it is above-mentioned
It in solution, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:1.5；Butyl titanate and microporous molecular
The mass ratio of sieve is 1:32, stirs evenly, is stored at room temperature；The resulting substance of above-mentioned steps is put into two mouth flask, and in room
It is passed through steam treatment 4h under temperature, transfers in Muffle furnace, is warming up to 550 in air atmosphere with the speed of 10 DEG C/min
DEG C, and 4h is kept at this temperature, room temperature is subsequently reduced to get required titanium oxide modified micropore molecular sieve shape selective catalysis is arrived
Agent is denoted as CAT3.
Embodiment 4
Butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve MCM-22 is added to it is above-mentioned
It in solution, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:1；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:20, stir evenly, be stored at room temperature；The resulting substance of above-mentioned steps is put into two mouth flask, and in room temperature
Under be passed through steam treatment 4h, transfer in Muffle furnace, be warming up to 550 DEG C in air atmosphere with the speed of 10 DEG C/min,
And 4h is kept at this temperature, room temperature is subsequently reduced to get to required titanium oxide modified micropore molecular sieve shape-selective catalyst, is remembered
For CAT4.
Embodiment 5
Butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve MCM-22 is added to it is above-mentioned
It in solution, stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:2；Butyl titanate and micro porous molecular sieve
Mass ratio be 1:9, stir evenly, be stored at room temperature；The resulting substance of above-mentioned steps is put into two mouth flask, and at room temperature
It is passed through steam treatment 3h, is transferred in Muffle furnace, is warming up to 550 DEG C in air atmosphere with the speed of 10 DEG C/min, and
4h is kept at this temperature, is subsequently reduced to room temperature to get to required titanium oxide modified micropore molecular sieve shape-selective catalyst, is denoted as
CAT5。
Obtained titanium oxide modified micropore molecular sieve in above-described embodiment is used for toluene and dimethyl carbonate is alkylated
During at paraxylene, typical reaction condition are as follows: 400 DEG C of reaction temperature, material quality air speed is 0.8h-1, 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 |
As 1 result of table as it can be seen that titanium oxide modified micropore 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 (1)
1. a kind of titanium oxide modified micropore molecular sieve shape-selective catalyst is combined to paraxylene in toluene and dimethyl carbonate alkyl
In application, it is characterised in that the specifically used method of the catalyst is:
It is 400 DEG C of reaction temperature, former using titanium oxide modified micropore molecular sieve as catalyst using toluene and dimethyl carbonate as raw material
Material mass space velocity is 0.8h-1, successive reaction 8h, wherein titanium oxide modified micropore molecular sieve the preparation method is as follows:
(1) butyl titanate is added in dehydrated alcohol, it is to be mixed uniformly after micro porous molecular sieve is added in above-mentioned solution,
It stirs evenly, wherein the mass ratio of butyl titanate and dehydrated alcohol is 1:1-1:2；The matter of butyl titanate and micro porous molecular sieve
Amount is stirred evenly, is stored at room temperature than being 1:9-1:32；
(2) step (1) resulting substance is put into two mouth flask, 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, then dropped
To room temperature to get required titanium oxide modified micropore molecular sieve shape-selective catalyst is arrived, the content of titanium oxide is catalysis in catalyst
The 3%~10% of agent gross mass, the micro porous molecular sieve are ZSM-5 or MCM-22.
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Citations (4)
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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 |
| CN105198691A (en) * | 2015-09-08 | 2015-12-30 | 山东成泰化工有限公司 | Synthesis method for p-xylene |
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- 2016-12-06 CN CN201611106137.0A patent/CN106582787B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105198691A (en) * | 2015-09-08 | 2015-12-30 | 山东成泰化工有限公司 | Synthesis method for p-xylene |
Non-Patent Citations (1)
| Title |
|---|
| 负载型TiO2/ZSM－5 的制备及其光催化降解亚甲基蓝;罗明汉等;《环境工程》;20141231;第32卷;288页1.2部分 * |
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