CN102872904A - Method for preparing shape-selective catalyst - Google Patents
Method for preparing shape-selective catalyst Download PDFInfo
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- CN102872904A CN102872904A CN2012103886551A CN201210388655A CN102872904A CN 102872904 A CN102872904 A CN 102872904A CN 2012103886551 A CN2012103886551 A CN 2012103886551A CN 201210388655 A CN201210388655 A CN 201210388655A CN 102872904 A CN102872904 A CN 102872904A
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- shape
- molecular sieve
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- melamine
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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
Abstract
The invention relates to a method for preparing a shape-selective catalyst. According to the method, a microhole molecular sieve ZSM-5 or MCM-22 is taken as a matrix; melamine is used as a precursor; carbon nitride (C3N4) is loaded on the outer surface of the microhole molecular sieve through immersing and calcining; during immersing, dimethyl sulfoxide (DMSO) is used as a solvent; and the mass ratio of melamine to the microhole molecular sieve is 1:1-1:5. The method has the advantages of simplicity, low cost, high shape-selective performance and the like; the acid site on the outer surface of the molecular sieve can be completely covered; and therefore, the shape-selective performance of the microhole molecular sieve is improved.
Description
Technical field
The present invention relates to the preparation field of alkylation process high performance catalyst, particularly a kind of for the synthesis of the preparation method to alkylphenol or p dialkyl benzene process shape-selective catalyst.
Background technology
Alkylphenol is widely used in producing the key areas such as phenolic resins, rubber anti-ageing agent, surfactant, but also is the important intermediate of producing spices and agricultural chemicals.Synthetic method to alkylphenol mainly contains natural partition method, methylaniline diazotising Hydrolyze method, methylbenzene chlorinolysis and alkylation of phenol method.Wherein first three methods is owing to complex process, and the not high reason of production process seriously corroded and product quality is eliminated gradually, and the alkylation of phenol method is the focus of studying at present.P dialkyl benzene also is important industrial chemicals, and its traditional synthetic method mainly is to obtain by the toluene disproportionation process, but because dismutation needs stronger acidic catalyst and higher reaction temperature, so catalysqt deactivation is very fast.Become in recent years the focus of research by the synthetic p dialkyl benzene of toluene direct alkylation process.
Yet, catalyst commonly used in the alkylated reaction of phenol and toluene is the micro porous molecular sieves such as ZSM-5 or MCM-22, the result obtains the mixture that three kinds of alkyl replace often, for high selectivity obtain just must carry out modification to catalyst to alkylphenol or p dialkyl benzene.The purpose of modification mainly contains 2 points: the one, reduce the acidic site quantity of catalyst outer surface, and reduce product to the isomerization reaction at outer surface of alkylphenol or p dialkyl benzene; The 2nd, dwindle molecular sieve bore diameter, increase ortho position and a position alkylphenol or the diffusional resistance of dialkyl benzene in the hole.Usually modification has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre-carbon distribution and metal oxide modified.Although the Shape-selective that the method for siliceous deposits can the Effective Raise molecular sieve catalyst, but because the active force between molecular sieve surface hydroxyl and the deposit is very weak, often need 3 ~ 4 times deposition just can reach preferably 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 the 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 metal oxide modified to cover the operation of molecular sieve outer surface acidity position very simple, and once just can finish preferably and to cover, but the method also can cause the reduction of duct inner acidic when reducing outer surface acidity, therefore also fails to use on a large scale.The present invention is used for the new material carbonitride preparation of shape-selective catalyst first, because the predecessor melamine that uses in preparation carbonitride process has larger molecular dimension, therefore in dipping process, can effectively prevent it from entering in the molecule sieve aperture and affect its inner acidic position, hole, and melamine is conventional industrial chemicals, wide material sources, therefore the method is simple to operate, once just can realize the fully covering of outer surface acidity position, and the preparation cost of catalyst is cheap.
Summary of the invention
The technical problem to be solved in the present invention is for synthetic loaded down with trivial details to the preparation manipulation of shape-selective catalyst in alkylphenol and the p dialkyl benzene process, cost is high, and the problem such as Shape-selective is not high, provides a kind of synthetic method simple, shape-selective catalyst preparation method with low cost, that Shape-selective is high.
The technical solution adopted for the present invention to solve the technical problems is:
Take by weighing melamine; it is added in the dimethyl sulfoxide (DMSO); wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5; being warming up to 50 ℃ dissolves it fully; then micro porous molecular sieve is added in the mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:1 ~ 1:5; stir; room temperature leaves standstill to be put under 80 ℃ of water-baths behind the 24h dries; be transferred to subsequently 110 ℃ of dry 6h in the air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst.
As limitation of the invention, micro porous molecular sieve of the present invention is ZSM-5 or MCM-22.
Shape-selective catalyst of the present invention can be applied in the synthetic process to alkylphenol and p dialkyl benzene; Especially be fit to be applied in the process of synthetic p-methyl phenol and paraxylene.
The present invention first take melamine as presoma by flood and the method for roasting with carbonitride (C
3N
4) be carried on the micro porous molecular sieve outer surface, both can effectively cover the acidic site of molecular sieve outer surface, can protect again its inner acidic position, hole unaffected, when keeping higher catalyst activity, the Shape-selective of catalyst is further improved.Therefore has the preparation method relatively simple, with low cost, the Shape-selective advantages of higher.
The specific embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the usefulness for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
Take by weighing melamine (3g), it is added in the dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved fully.Then 3g micro porous molecular sieve MCM-22 is added in the mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:1; stir; room temperature leaves standstill to be put under 80 ℃ of water-baths behind the 24h dries; be transferred to subsequently 110 ℃ of lower dry 6h in the air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst Cat1.
Embodiment 2
Take by weighing melamine (3g), it is added in the dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved fully.Then 15g micro porous molecular sieve MCM-22 is added in the mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:5; stir; room temperature leaves standstill to be put under 80 ℃ of water-baths behind the 24h dries; be transferred to subsequently 110 ℃ of lower dry 6h in the air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst Cat2.
Embodiment 3
Take by weighing melamine (3g), it is added in the dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved fully.Then 9g micro porous molecular sieve MCM-22 is added in the mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:3; stir; room temperature leaves standstill to be put under 80 ℃ of water-baths behind the 24h dries; be transferred to subsequently 110 ℃ of lower dry 6h in the air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst Cat3.
Embodiment 4
Take by weighing melamine (3g), it is added in the dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved fully.Then 9g micro porous molecular sieve ZSM-5 is added in the mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:3; stir; room temperature leaves standstill to be put under 80 ℃ of water-baths behind the 24h dries; be transferred to subsequently 110 ℃ of lower dry 6h in the air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst Cat4.
Catalyst in above-described embodiment is used for the process of phenol and the synthetic p-methyl phenol of dimethyl carbonate alkylation, the typical reaction condition is: phenol and dimethyl carbonate mol ratio are 1:1, and 360 ℃ of reaction temperatures, material quality air speed are 2h
-1, estimate continuously 8h.The catalytic performance of each catalyst is as shown in table 1:
The catalytic performance of table 1 catalyst
| Catalyst | Phenol conversion (%) | P-methyl phenol selective (%) |
| Cat1 | 91.6 | 47.4 |
| Cat2 | 75.3 | 76.1 |
| Cat3 | 82.8 | 72.9 |
| Cat4 | 71.7 | 75.5 |
Again the catalyst in above-described embodiment is applied to the synthetic paraxylene of fixed bed reactors, namely uses toluene and dimethyl carbonate as raw material.The typical reaction condition is: toluene and dimethyl carbonate mol ratio 4:1, and instead it answers 380 ℃ of temperature, and reaction pressure is normal pressure, and raw material toluene mass space velocity is 1h
-1, estimate continuously 12h.The catalytic performance of each catalyst is as shown in table 2:
The catalytic performance of table 2 catalyst
| Catalyst | Toluene conversion (%) | Selectivity for paraxylene (%) |
| Cat1 | 32.2 | 31.6 |
| Cat2 | 20.9 | 77.4 |
| Cat3 | 25.7 | 70.1 |
| Cat4 | 22.8 | 72.3 |
Can find out from table 1 and table 2, catalyst of the present invention is applied in the building-up process of p-methyl phenol and paraxylene, p-methyl phenol selectively reach as high as 75.5%, paraxylene selectively reach as high as 77.4%, reached and well selected the shape effect; And method for preparing catalyst of the present invention is simple, and is with low cost, is a kind of desirable catalyst with high Shape-selective.
Take above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, the relevant staff can in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on the specification, must determine its technical scope according to the claim scope.
Claims (4)
1. the preparation method of a shape-selective catalyst is characterized in that the method carries out according to following step:
(1) take by weighing a certain amount of melamine, it is added in the dimethyl sulfoxide (DMSO), the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is heated to 50 ℃ it is dissolved fully;
(2) then in the solution of step (1) gained, add micro porous molecular sieve; the mass ratio of melamine and micro porous molecular sieve is 1:1 ~ 1:5; stir; room temperature leaves standstill 24h and is placed under 80 ℃ of water-baths and dries; be transferred to subsequently 110 ℃ of dry 6h of air dry oven, put into again the Muffle furnace roasting, make protection gas with argon gas; be warming up to 500 ℃ with 3 ℃/min and keep 4h, obtain required shape-selective catalyst.
2. the preparation method of a kind of 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 shape-selective catalyst according to claim 1 is characterized in that described shape-selective catalyst can be applied in the synthetic process to alkylphenol and p dialkyl benzene.
4. the preparation method of a kind of shape-selective catalyst according to claim 3, it is characterized in that described is p-methyl phenol to alkylphenol, described p dialkyl benzene is paraxylene.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381371A (en) * | 2013-07-16 | 2013-11-06 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN103638961A (en) * | 2013-12-25 | 2014-03-19 | 重庆工商大学 | Preparation method of supported carbon nitride photo-catalyst |
| CN103755383A (en) * | 2014-01-24 | 2014-04-30 | 福建农林大学 | Functional stone slab immobilized with graphite phase carbon nitride and preparation method of functional stone slab |
| CN106673968A (en) * | 2016-12-22 | 2017-05-17 | 伊犁哈萨克自治州塔城地区人民医院 | Method of synthesizing veratrole |
| CN107029774A (en) * | 2017-03-20 | 2017-08-11 | 暨南大学 | A kind of preparation method and applications of nanoporous class graphitic carbonaceous nitrogen material |
| CN107716119A (en) * | 2017-09-26 | 2018-02-23 | 中国科学院青海盐湖研究所 | A kind of floatating agent of sodium chloride and preparation method thereof |
| CN108636444A (en) * | 2018-04-25 | 2018-10-12 | 常州大学 | A kind of preparation method for dismutation shape-selective catalyst |
| CN108772097A (en) * | 2018-07-02 | 2018-11-09 | 西北大学 | A kind of preparation method of metal-solids soda acid multifunctional core shell catalyst |
| CN108940353A (en) * | 2018-07-02 | 2018-12-07 | 西北大学 | A kind of method of one-step synthesis solid acid-base bifunctional nucleocapsid catalyst |
| CN109772437A (en) * | 2019-02-18 | 2019-05-21 | 渤海大学 | A kind of method and application that ZSM-5 molecular sieve surface is modified |
| CN111871448A (en) * | 2020-08-03 | 2020-11-03 | 西北大学 | Catalyst for improving oxygen-free aromatization reaction performance of methane and preparation method thereof |
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| US20070149384A1 (en) * | 2005-12-22 | 2007-06-28 | Saudi Basic Industries Corporation | Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof |
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Patent Citations (2)
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Non-Patent Citations (1)
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| CN103381371B (en) * | 2013-07-16 | 2015-07-01 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN103381371A (en) * | 2013-07-16 | 2013-11-06 | 常州大学 | Preparation method of carbon nitride/microporous molecular sieve composite material |
| CN103638961A (en) * | 2013-12-25 | 2014-03-19 | 重庆工商大学 | Preparation method of supported carbon nitride photo-catalyst |
| CN103638961B (en) * | 2013-12-25 | 2015-12-30 | 重庆工商大学 | A kind of preparation method of support type carbon nitride photocatalyst |
| CN103755383A (en) * | 2014-01-24 | 2014-04-30 | 福建农林大学 | Functional stone slab immobilized with graphite phase carbon nitride and preparation method of functional stone slab |
| CN103755383B (en) * | 2014-01-24 | 2016-04-27 | 福建农林大学 | Functional stone slab of a kind of immobilized graphite phase carbon nitride and preparation method thereof |
| CN106673968A (en) * | 2016-12-22 | 2017-05-17 | 伊犁哈萨克自治州塔城地区人民医院 | Method of synthesizing veratrole |
| CN106673968B (en) * | 2016-12-22 | 2020-01-14 | 伊犁哈萨克自治州塔城地区人民医院 | Method for synthesizing veratrole |
| CN107029774B (en) * | 2017-03-20 | 2019-10-18 | 暨南大学 | A kind of preparation method and applications of nanoporous class graphitic carbonaceous nitrogen material |
| CN107029774A (en) * | 2017-03-20 | 2017-08-11 | 暨南大学 | A kind of preparation method and applications of nanoporous class graphitic carbonaceous nitrogen material |
| CN107716119A (en) * | 2017-09-26 | 2018-02-23 | 中国科学院青海盐湖研究所 | A kind of floatating agent of sodium chloride and preparation method thereof |
| CN107716119B (en) * | 2017-09-26 | 2020-04-10 | 中国科学院青海盐湖研究所 | Preparation method of sodium chloride flotation agent |
| CN108636444A (en) * | 2018-04-25 | 2018-10-12 | 常州大学 | A kind of preparation method for dismutation shape-selective catalyst |
| CN108940353A (en) * | 2018-07-02 | 2018-12-07 | 西北大学 | A kind of method of one-step synthesis solid acid-base bifunctional nucleocapsid catalyst |
| CN108772097A (en) * | 2018-07-02 | 2018-11-09 | 西北大学 | A kind of preparation method of metal-solids soda acid multifunctional core shell catalyst |
| CN109772437A (en) * | 2019-02-18 | 2019-05-21 | 渤海大学 | A kind of method and application that ZSM-5 molecular sieve surface is modified |
| CN111871448A (en) * | 2020-08-03 | 2020-11-03 | 西北大学 | Catalyst for improving oxygen-free aromatization reaction performance of methane and preparation method thereof |
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