CN102872904B - Method for preparing shape-selective catalyst - Google Patents
Method for preparing shape-selective catalyst Download PDFInfo
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- CN102872904B CN102872904B CN201210388655.1A CN201210388655A CN102872904B CN 102872904 B CN102872904 B CN 102872904B CN 201210388655 A CN201210388655 A CN 201210388655A CN 102872904 B CN102872904 B CN 102872904B
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- molecular sieve
- 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
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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 to the key areas such as phenolic resins, rubber anti-ageing agent, surfactant, but also is the important intermediate of producing spices and agricultural chemicals.The synthetic method of alkylphenol is mainly contained to natural partition method, methylaniline diazotising Hydrolyze method, methylbenzene chlorinolysis and alkylation of phenol method.Wherein first three methods is due to complex process, and the not high reason of production process seriously corroded and product quality is eliminated gradually, and alkylation of phenol method is the focus of studying at present.P dialkyl benzene is also important industrial chemicals, and its traditional synthetic method is mainly to obtain by toluene disproportionation process, but because dismutation needs stronger acidic catalyst and higher reaction temperature, so catalysqt deactivation is very fast.By the synthetic p dialkyl benzene of toluene direct alkylation process, become in recent years the focus of research.
Yet, in the alkylated reaction of phenol and toluene, conventional catalyst is the micro porous molecular sieves such as ZSM-5 or MCM-22, result obtains the mixture that three kinds of alkyl replace often, for high selectivity obtain to alkylphenol or p dialkyl benzene, just must carry out modification to catalyst.The object of modification mainly contains 2 points: the one, reduce the acidic site quantity of catalyst outer surface, and reduce product isomerization reaction at outer surface to 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 hole.Conventionally the method for modification has chemical gaseous phase siliceous deposits, chemical liquid phase siliceous deposits, pre-carbon distribution and metal oxide modified.Although the method for siliceous deposits can effectively improve the Shape-selective of molecular sieve catalyst, but because the active force between molecular sieve surface hydroxyl and deposit is very weak, often need the deposition of 3 ~ 4 times just can reach good 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 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 complete good covering, but the method also can cause the reduction of duct inner acidic when reducing outer surface acidity, therefore also fail to use on a large scale.The present invention's preparation for shape-selective catalyst by new material carbonitride first, because the predecessor melamine using in preparing carbonitride process has larger molecular dimension, therefore in dipping process, can effectively prevent it from entering in 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 covering completely 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 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, Shape-selective is high.
The technical solution adopted for the present invention to solve the technical problems is:
Take melamine; added in dimethyl sulfoxide (DMSO); wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5; being warming up to 50 ℃ dissolves it completely; then micro porous molecular sieve is added in above-mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:1 ~ 1:5; stir; after the standing 24h of room temperature, be put under 80 ℃ of water-baths and dry; be transferred to subsequently 110 ℃ of dry 6h in air dry oven, then put into Muffle furnace roasting, with argon gas, make protection gas; with 3 ℃/min, be warming up to 500 ℃ 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 to synthetic in the process of alkylphenol and p dialkyl benzene; Especially be applicable to being applied in the process of synthetic p-methyl phenol and paraxylene.
The present invention be take first melamine and is passed through dipping and the method for roasting by carbonitride (C as presoma
3n
4) be carried on 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 maintaining higher catalyst activity, the Shape-selective of catalyst is further improved.Therefore there is preparation method relatively simple, with low cost, 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 use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
Take melamine (3g), added in dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved completely.Then 3g micro porous molecular sieve MCM-22 is added in above-mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:1; stir; after the standing 24h of room temperature, be put under 80 ℃ of water-baths and dry; be transferred to subsequently in air dry oven dry 6h at 110 ℃, then put into Muffle furnace roasting, with argon gas, make to protect gas; with 3 ℃/min, be warming up to 500 ℃ and keep 4h, obtain required shape-selective catalyst Cat1.
Embodiment 2
Take melamine (3g), added in dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved completely.Then 15g micro porous molecular sieve MCM-22 is added in above-mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:5; stir; after the standing 24h of room temperature, be put under 80 ℃ of water-baths and dry; be transferred to subsequently in air dry oven dry 6h at 110 ℃, then put into Muffle furnace roasting, with argon gas, make to protect gas; with 3 ℃/min, be warming up to 500 ℃ and keep 4h, obtain required shape-selective catalyst Cat2.
Embodiment 3
Take melamine (3g), added in dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved completely.Then 9g micro porous molecular sieve MCM-22 is added in above-mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:3; stir; after the standing 24h of room temperature, be put under 80 ℃ of water-baths and dry; be transferred to subsequently in air dry oven dry 6h at 110 ℃, then put into Muffle furnace roasting, with argon gas, make to protect gas; with 3 ℃/min, be warming up to 500 ℃ and keep 4h, obtain required shape-selective catalyst Cat3.
Embodiment 4
Take melamine (3g), added in dimethyl sulfoxide (DMSO), wherein the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is warming up to 50 ℃ it is dissolved completely.Then 9g micro porous molecular sieve ZSM-5 is added in above-mentioned solution; the mass ratio of melamine and micro porous molecular sieve is 1:3; stir; after the standing 24h of room temperature, be put under 80 ℃ of water-baths and dry; be transferred to subsequently in air dry oven dry 6h at 110 ℃, then put into Muffle furnace roasting, with argon gas, make to protect gas; with 3 ℃/min, be warming up to 500 ℃ and keep 4h, obtain required shape-selective catalyst Cat4.
Process by the catalyst in above-described embodiment for phenol and the synthetic p-methyl phenol of dimethyl carbonate alkylation, typical reaction condition is: phenol and dimethyl carbonate mol ratio are 1:1,360 ℃ of reaction temperatures, material quality air speed is 2h
-1, evaluate 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, uses toluene and dimethyl carbonate as raw material.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, evaluate 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 |
As can be seen 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 shape effect; And method for preparing catalyst of the present invention is simple, with low cost, be a kind of desirable catalyst with high Shape-selective.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to claim scope.
Claims (2)
1. for the synthesis of the preparation method to the shape-selective catalyst of alkylphenol and p dialkyl benzene, it is characterized in that the method carries out according to following step:
(1) take a certain amount of melamine, added in dimethyl sulfoxide (DMSO), the mass ratio of melamine and dimethyl sulfoxide (DMSO) is 1:5, is heated to 50 ℃ it is dissolved completely;
(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, the standing 24h of room temperature is placed under 80 ℃ of water-baths and dries, be transferred to subsequently 110 ℃ of dry 6h of air dry oven, then put into Muffle furnace roasting, with argon gas, make protection gas, with 3 ℃/min, be warming up to 500 ℃ and keep 4h, obtain required shape-selective catalyst; Described micro porous molecular sieve is ZSM-5 or MCM-22.
2. the preparation method of a kind of shape-selective catalyst according to claim 1, it is characterized in that described is p-methyl phenol to alkylphenol, described p dialkyl benzene is paraxylene.
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| CN201210388655.1A CN102872904B (en) | 2012-10-12 | 2012-10-12 | Method for preparing shape-selective catalyst |
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| CN102872904B true CN102872904B (en) | 2014-03-05 |
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111871448B (en) * | 2020-08-03 | 2021-06-18 | 西北大学 | Catalyst for improving oxygen-free aromatization reaction performance of methane and preparation method thereof |
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| US7662737B2 (en) * | 2005-12-22 | 2010-02-16 | Saudi Basic Industries Corporation | Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof |
| CN101121139A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Catalyst for methylbenzene shape selective disproportionation reaction to making para-xylene |
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