CN107626311A - A kind of preparation method and application of the supported copper nano-structured calalysts of KIT 6 - Google Patents
A kind of preparation method and application of the supported copper nano-structured calalysts of KIT 6 Download PDFInfo
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- CN107626311A CN107626311A CN201711075664.4A CN201711075664A CN107626311A CN 107626311 A CN107626311 A CN 107626311A CN 201711075664 A CN201711075664 A CN 201711075664A CN 107626311 A CN107626311 A CN 107626311A
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Abstract
The present invention relates to meso-porous nano structure and catalytic field, specifically a kind of preparation method of order mesoporous copper catalyst, the present invention has obvious advanced, the method one-step synthesis Cu/KIT 6 synthesized in the past compared with background technology, and catalyst is made using regulation pH to 8 12.This preparation method is simple to operate, and technique is advanced, and cost of material is low, and data are accurately full and accurate, and preparation speed is fast, is a kind of very good method for preparing methyl acetate preparation of ethanol by hydrogenating catalysts.The catalyst of order mesoporous Cu/KIT 6 of gained had both had the advantages that the high activity advantage that a kind of raw material is cheap and easy to get and preparation process is simplified, and has nanocrystal catalysis again, was a kind of good nanocatalyst.
Description
Technical field
The present invention relates to meso-porous nano structure and catalytic field, specifically a kind of preceding synthetic method prepares KIT-6 supported coppers and received
The preparation method of rice structure catalyst and its catalytic effect for methyl acetate preparation of ethanol through hydrogenation, the preparation method are relatively simple
It is single, the strong excellent catalytic effect of catalyst product activity of acquisition.
Background technology
With increasingly deficient and price the continuous rise of Global Oil resource, alcohol fuel is used as one kind is free of contamination to replace
There is extraordinary application prospect and value for performance source, methyl acetate preparation of ethanol by hydrogenating technology receives more and more attention.
China's methyl acetate demand is limited, and a large amount of industrialized production methyl acetates make methyl acetate industry face production capacity surplus and city
The low predicament in field, therefore methyl acetate how is effectively utilized, environmental protection pressure is reduced, is always that domestic relevant industries are urgently to be resolved hurrily
The problem of.The state of methyl acetate production capacity surplus can thus be improved using methyl acetate preparation of ethanol by hydrogenating, alleviate enterprise and ring
Border pressure, therefore methyl acetate catalysis preparation of ethanol through hydrogenation is significant, efficient pollution-free catalyst in catalytic hydrogenation
Using being one of approach for realizing the target.In recent years, the research of mesopore molecular sieve obtains very big development, and it has huge
Specific surface area, adjustable aperture, high thermal stability and hydrothermal stability make it potential application value be present in many fields.
KIT-6 is a kind of orderly meso-hole structure of three-dimensional cubic, and aperture is relatively large, adjustable between 4-12nm, and it is distinctive three
Cube duct makes the load of active specy become easy, and loaded article can be whole just as the mesoporous template of an opening
Duct inner dispersion is uniformly without forming the bulky grain reunited.Patent CN103240095 is using cupro-nickel as composite reactive component, alkali
One or more in earth metal, transition metal and rare earth metal are co-catalyst, and used carrier is aluminum oxide, and it is in fixed bed
In production technology, the conversion ratio of methyl acetate is up to 82%, ethanol selectivity 90%.
KIT-6 has the orderly meso-hole structure of three-dimensional cubic, and its huge specific surface area, adjustable aperture, high fever are steady
Qualitative and hydrothermal stability makes it be developed well in catalytic field.Method for preparing catalyst of the present invention is preceding conjunction
KIT-6 supported copper meso-porous nano structure catalysts are synthesized into method, high activity is shown in methyl acetate hydrogenation process.
The content of the invention
The present invention is intended to provide a kind of Jie with high activity and high selectivity for methyl acetate preparation of ethanol through hydrogenation
Hole nano-structured calalyst, specifically a kind of preceding synthetic method prepare KIT-6 supported copper nano-structured calalysts.
The present invention is achieved by the following technical solutions：A kind of preparation side of KIT-6 supported coppers nano-structured calalyst
Method, comprise the following steps：
（1）It is according to material molar ratio by tetraethyl orthosilicate TEOS, P123, hydrochloric acid, copper nitrate solution, n-butanol and deionized water
1：0.02：1.85：0.05：1.13：195 are added, and 24h is stirred at 35 DEG C；
（2）Solution is kept for 48 hours under 95 DEG C of vacuum conditions；
（3）Adjust pH to 8-12, filtering, 100 DEG C of dryings overnight；
（4）By dried product under 550 DEG C of environment, 6h is calcined under air atmosphere, KIT-6 supported copper nanostructureds is obtained and urges
Agent.
In the present invention, the tetraethyl orthosilicate TEOS provides silicon source for the preparation of catalyst.P123 is a kind of surface
Activating agent, there is adjustment to the form of catalyst.Being used for of hydrochloric acid adjusts pH, and to the structure and form of catalyst
There is adjustment.Copper nitrate solution provides copper source for catalyst.N-butanol can be to catalyst structural adjustment generation three
Tie up ordered mesopore structure.It can be prepared using material molar ratio of the present invention and generate the catalyst more copper-loaded than more complete KIT-6, and
And better catalytic activity.
It is prepared invention further provides a kind of preparation method of KIT-6 supported coppers nano-structured calalyst
Application of the KIT-6 supported coppers nano-structured calalyst in methyl acetate preparation of ethanol through hydrogenation.
As the further improvement of application technology scheme of the present invention, the reaction condition of application：Reaction temperature is 250 DEG C, instead
It is 3.0MPa to answer pressure, and the mass space velocity of methyl acetate is 1.5h-1, the volume space velocity 1500h of hydrogen-1。
The present invention is using tetraethyl orthosilicate, P123, hydrochloric acid, copper nitrate solution, n-butanol and deionized water as raw material, by advance
The step of ratio one set assembles synthesis Cu/KIT-6 catalyst altogether.Rather than traditional silica or other carriers pass through
Catalyst prepared by the conventional method such as dipping and ion exchange.Preceding synthetic method is a kind of relatively easy novel method, in hydro-thermal
Cu is supported in cell walls during synthesis KIT-6, and Cu loaded articles can be in whole duct inner dispersion uniformly without the group of being formed
Poly- bulky grain.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the X ray diffracting spectrum of KIT-6 supported copper nanocrystalline catalysts, in figure：Ordinate is diffracted intensity, horizontal
Coordinate is the θ of the angle of diffraction 2, and base peak is copper simple substance characteristic diffraction peak.
Fig. 2 is the BET phenograms of KIT-6 supported copper nanocrystalline catalysts.
Fig. 3 is gas phase hydrogenation reaction apparatus structure schematic diagram.In figure：1-H2, 2- pressure regulator valves, 3- flowmeters, 4- vaporizers,
5- furnace reactors, 6- condensation chambers, 7- constant-flux pumps, 8- raw material methyl acetates.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned
Other embodiment, belong to the scope that the present invention is protected.
Technical scheme is described in detail below in conjunction with the accompanying drawings.
The chemical substance material used during specific implementation is：Tetraethyl orthosilicate TEOS, P123, hydrochloric acid, copper nitrate solution and
Deionized water.Its dosage is with mole for measurement unit.
Tetraethyl orthosilicate TEOS liquid 1mol
P123 vaseline shapes 0.02mol
Hydrochloric acid HCL liquid contains hydrochloric acid 1.85mol
Copper nitrate solution Cu (NO)2Liquid contains copper nitrate 0.05mol
N-butanol liquid 1.13mol
Deionized water liquid 195mol
Preparation method is as follows：
1st, the preparation of KIT-6 copper-loading catalysts
（1）Add 1mol tetraethyl orthosilicate TEOS, 0.02molP123,1.85mol hydrochloric acid, copper nitrate solution（Copper nitrate
0.05mol）, 1.13mol n-butanols and 195mol deionized waters, stir 24h at 35 DEG C.
（2）Vacuum condition at 95 DEG C of solution is kept for 48 hours.
（3）Adjust pH to 8, filtering, 100 DEG C of dryings overnight.
（4）Sample is moved in tube furnace, 550 DEG C is risen to 2 DEG C/min speed, 6h is calcined under air atmosphere.
2nd, weigh, count
Cu/KIT-6 is placed on pan paper, weighed using electronic analytical balance, and record data；The catalyst that will be prepared
It is fitted into sample sack, posts label, is placed in drier, closed preservation；
3rd, detect, analyze and characterize
Crystal phase analysis is carried out with X-ray powder diffraction instrument to the Cu/KIT-6 catalyst of preparation；The specific surface area of catalyst, hole
Footpath is distributed and the analysis of pore volume is carried out on Quadrasorb SI, records the adsorption/desorption curve of catalyst.In test
Before, sample is deaerated 3 h under 573 K first.Analysis to its specific surface area uses Bruuauer-Emmett-Teller
(BET) method.Pore-size distribution uses Barrett-Joyner-Halenda (BJH) model.Show the N of catalyst2Absorption
Desorption curve, curve belong to Langmuir IV types, and sluggish ring-shaped belongs to H2 types, as shown in Figure 2.This result shows, urges
Agent has preferable meso-hole structure.
The 3 h purpose of being deaerated before test to sample under 573 K is the moisture of catalyst surface and other are miscellaneous
Matter is gone out, to carry out absorption representation specific surface area.
4th, catalytic performance test
Estimation of stability is carried out to gained catalyst using methyl acetate gas phase hydrogenation reaction device-fixed bed reactors.
Above-mentioned catalyst 3.0g is taken, using methyl acetate as raw material, the catalytic hydrogenation in fixed bed reactors, reaction condition
For：Reaction temperature is 250 DEG C, reaction pressure 3.0MPa, and the mass space velocity of methyl acetate is 1.5h-1, the volume space velocity of hydrogen
1500h-1.Chromatography is sampled, methyl acetate conversion ratio is 95%, and the selectivity of ethanol is 92%.
When it is implemented, step（3）Any pH value that middle pH can tune between 8-12, using other in the range of this
Meaning pH value（Such as 10,12）The influence of significant adverse can't be produced to the performance of catalyst.But outside this scope
Other pH value, catalyst performance can be had an impact, or even influence structural behaviour.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (3)
1. a kind of preparation method of KIT-6 supported coppers nano-structured calalyst, it is characterised in that comprise the following steps：
（1）It is according to material molar ratio by tetraethyl orthosilicate TEOS, P123, hydrochloric acid, copper nitrate solution, n-butanol and deionized water
1：0.02：1.85：0.05：1.13：195 are added, and 24h is stirred at 35 DEG C；
（2）Solution is kept for 48 hours under 95 DEG C of vacuum conditions；
（3）Adjust pH to 8-12, filtering, 100 DEG C of dryings overnight；
（4）By dried product under 550 DEG C of environment, 6h is calcined under air atmosphere, KIT-6 supported copper nanostructureds is obtained and urges
Agent.
2. the KIT-6 loads that a kind of preparation method of KIT-6 supported coppers nano-structured calalyst described in claim 1 is prepared
Application of the copper nano-structured calalyst in methyl acetate preparation of ethanol through hydrogenation.
3. application as claimed in claim 2, it is characterised in that the reaction condition of application：Reaction temperature is 250 DEG C, reaction pressure
Power is 3.0MPa, and the mass space velocity of methyl acetate is 1.5h-1, the volume space velocity 1500h of hydrogen-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109794249A (en) * | 2019-01-25 | 2019-05-24 | 太原理工大学 | A kind of preparation method of laminar silicic acid copper-zinc nano piece |
Citations (3)
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|---|---|---|---|---|
| CN102139213A (en) * | 2010-02-03 | 2011-08-03 | 中国科学院福建物质结构研究所 | Preparation method for synthesizing catalyst of ethylene glycol by sol-gel method and operation method |
| KR101294100B1 (en) * | 2012-02-01 | 2013-08-07 | 한국에너지기술연구원 | Manufacturing method for alloy and metal supported catalysts using sequential melt-infiltration process and alloy and hybrid metal supported catalyst thereof |
| CN104148086A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst and method for preparing ethanol |
-
2017
- 2017-11-06 CN CN201711075664.4A patent/CN107626311A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139213A (en) * | 2010-02-03 | 2011-08-03 | 中国科学院福建物质结构研究所 | Preparation method for synthesizing catalyst of ethylene glycol by sol-gel method and operation method |
| KR101294100B1 (en) * | 2012-02-01 | 2013-08-07 | 한국에너지기술연구원 | Manufacturing method for alloy and metal supported catalysts using sequential melt-infiltration process and alloy and hybrid metal supported catalyst thereof |
| CN104148086A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst and method for preparing ethanol |
Non-Patent Citations (2)
| Title |
|---|
| BAITAO LI等: ""One-pot synthesis of ordered mesoporous Cu-KIT-6 and its improved catalytic behavior for the epoxidation of styrene: Effects of the pH value of the initial gel", 《CHINESE JOURNAL OF CATALYSIS》 * |
| JIAN SUN等: "Different transition metal (Fe2+, Co2+, Ni2+, Cu2+ or VO2+) Schiff complexes immobilized onto three-dimensional mesoporous silica KIT-6 for the epoxidation of of styrene", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109794249A (en) * | 2019-01-25 | 2019-05-24 | 太原理工大学 | A kind of preparation method of laminar silicic acid copper-zinc nano piece |
| CN109794249B (en) * | 2019-01-25 | 2021-11-19 | 太原理工大学 | Preparation method of layered copper zinc silicate nanosheet |
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