CN109603826A - Copper-carbon/silica/ceramic monolith catalyst and preparation method thereof - Google Patents
Copper-carbon/silica/ceramic monolith catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of copper-carbon/silica/ceramic monolith catalyst and preparation method thereof, comprising the following steps: nonloaded silica obtains silica/ceramic monolith on ceramic monolith；Copper salt solution and strong base solution are mixed to get copper hydroxide suspension；Trimesic acid solution is mixed with copper hydroxide suspension, ultrasound, is separated by solid-liquid separation；It is dispersed in water after separating obtained solid is washed to neutrality, adjusting pH value using weak base is 10~13, obtains cupric ammine complex solution；Silica/ceramic monolith is immersed in cupric ammine complex solution, heating reaction is carried out, obtains solid composite after separating, washing to neutrality；By solid composite calcining, reduction activation, copper-carbon/silica/ceramic monolith catalyst is obtained.Preparation process of the present invention is simple, and preparation condition is mild, environmental-friendly, significantly reduces production cost, is expected to be widely applied in industrialized production, have broad application prospects.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of copper-carbon/silica/ceramic monolith is urged
Agent and preparation method thereof.
Background technique
Currently, the copper-based catalysts for being commercially used for hydrogenation reaction mostly use infusion process, the precipitation method, ammonia still process method etc. traditional
Carrying method preparation.Traditional carrying method process is relatively complicated, and method preparation process is complicated and is not directed to carbon modification work
Process, preparation process is related to the high cost reagent such as soluble rare earth metal, high expensive, while shaping of catalyst method is certain
Its industrial applications is limited in degree.Therefore, exploitation preparation method is easy and the integral catalyzer that has excellent performance, to meeting work
Industry application demand is significant.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of copper-carbon/silica/ceramics are whole
Body formula catalyst and preparation method thereof, at least be partially solved at least one of above problem.
The present invention is achieved through the following technical solutions:
As one aspect of the present invention, a kind of copper-carbon/silica/ceramic monolith catalyst is provided, including following
Step:
(1) nonloaded silica obtains silica/ceramic monolith on ceramic monolith；
(2) copper salt solution and strong base solution are mixed to get copper hydroxide suspension；
(3) trimesic acid solution is mixed, ultrasound with the copper hydroxide suspension, the mixed liquor after ultrasound is consolidated
Liquid separation；
(4) be dispersed in water after washing step (3) separating obtained solid to neutrality, using weak base adjust pH value be 10~
13, obtain cupric ammine complex solution；
(5) silica for obtaining step (1)/ceramic monolith immerses in the cupric ammine complex solution, is adding
It is reacted under hot pressurized conditions, obtains solid composite after separating, washing to neutrality；
(6) solid composite for obtaining step (5) is calcined, and then reduction activation in reducing atmosphere, obtains
Copper-carbon/silica/ceramic monolith catalyst.
According to another aspect of the present invention, a kind of copper-carbon/dioxy that preparation method as described above is prepared is provided
SiClx/ceramic monolith catalyst, it is copper-based relative to silica in the copper-carbon/silica/ceramic monolith catalyst
Load capacity be 0.5~40wt%, carbon phase for silica load capacity be 0.1~10%, surplus is carrier.
It can be seen from the above technical proposal that copper-carbon/silica/ceramic monolith catalyst of the present invention and its preparation
Method has the advantages that
(1) present invention utilizes one step of ultrasonic method that Cu in conjunction with component C, is made the mutual close cooperation of Cu, C, and loaded
To carrier, the copper-carbon/silica/ceramic monolith catalyst for being easier to industrial applications has been obtained, has been catalyzed for copper metal
The preparation of agent provides new means.
(2) present invention, which passes through metal framework derivative and is loaded to ceramic hydrolysis methods, is prepared for copper-carbon/titanium dioxide
Silicon/ceramic monolith catalyst.The preparation process is simple, and reaction condition is mild, environmental-friendly, effectively reduces and is produced into
This, is expected to be widely applied in industrialized production, have broad application prospects.
Detailed description of the invention
Fig. 1 is 1 bronze medal of the embodiment of the present invention-carbon/silica/ceramic monolith catalyst SEM figure.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The present invention provides a kind of copper-carbon/silica/ceramic monolith catalyst and preparation method thereof, pass through metal
Frame is derivative and is loaded to silica/ceramic monolith hydrolysis methods, and it is whole that copper-carbon/silica/ceramics are prepared
Formula catalyst, preparation process is simple, and reaction condition is mild, environmental-friendly, effectively reduces production cost, is expected to widely answer
It uses in industrialized production, has broad application prospects.
Specifically, as one aspect of the present invention, a kind of copper-carbon/silica/ceramic monolith catalyst is provided
Preparation method, comprising the following steps:
(1) nonloaded silica obtains silica/ceramic monolith on ceramic monolith；
(2) copper salt solution and strong base solution are mixed to get copper hydroxide suspension；
(3) trimesic acid solution is mixed, ultrasound with the copper hydroxide suspension, the mixed liquor after ultrasound is consolidated
Liquid separation；
(4) be dispersed in water after washing step (3) separating obtained solid to neutrality, using weak base adjust pH value be 10~
13, obtain cupric ammine complex solution；
(5) silica for obtaining step (1)/ceramic monolith immerses in the cupric ammine complex solution, is adding
It is reacted under hot pressurized conditions, obtains solid composite after separating, washing to neutrality；
(6) solid composite for obtaining step (5) is calcined, and then reduction activation in reducing atmosphere, obtains
Copper-carbon/silica/ceramic monolith catalyst.
Step (1) specifically includes following sub-step:
Sub-step (1a): dry after ceramic monolith is ultrasonically treated in acid solution；
Sub-step (1b): it after sonicated ceramic monolith is calcined, is dipped in silicon source solution for a period of time, uses gas
Body purges redundant solution and drying；
Sub-step (1c): repeat sub-step (1a) to load capacity of the silica on ceramic monolith reach 0.1mg~
2mg/mm3After be dried, calcine.
In sub-step (1a), ceramic monolith is one of cordierite ceramic, zirconia ceramics and aluminium oxide ceramics or two
Kind or more combination；Acid solution is nitric acid and/or sulfuric acid, and concentration is 5%~30%；Ultrasonic temperature is 20~60 DEG C, the time
For 0.5~5h；Drying temperature be 50~150 DEG C, the time be 5~for 24 hours.This step can remove pottery by the pretreatment of acid solution
The substances such as iron, titanium, sodium, potassium, calcium, magnesium in ceramic carrier, in order to avoid influence the load of silica on it.
In sub-step (1b), calcination temperature is 200~800 DEG C, 1~8h of time；Silicon source is silica solution and/or positive silicic acid
Ester, the positive esters of silicon acis can be methyl orthosilicate or ethyl orthosilicate etc.；Soaking time is 0.5~2h；Purge gas be air,
The combination of one or more of nitrogen and argon gas；Drying temperature is 80~150 DEG C, the time 2~for 24 hours.
In sub-step (1c), drying temperature is 80~150 DEG C, the time 3~for 24 hours；Calcination temperature is 200~800 DEG C, the time
1~8h.
In step (2), copper salt solution is obtained by the way that copper source is dissolved in the water, and copper source is copper nitrate, copper sulphate, copper chloride
With the combination of one or more of copper acetate；Strong base solution is obtained by the way that alkali source is dissolved in the water, and alkali source is hydrogen-oxygen
Change sodium and/or potassium hydroxide.
In step (3), trimesic acid solution is made by the way that trimesic acid to be dissolved in ethyl alcohol；Ultrasonic temperature is 20
~60 DEG C, ultrasonic time is 0.5~6h；
In step (4), weak base is ammonium hydroxide or carbonic acid ammonium, this step is conducive to what copper and trimesic acid were formed using weak base
Complex salt is loaded on silica/ceramic monolith, and highly basic is unfavorable for its load.
In step (5), soaking time of the silica/ceramic monolith in cupric ammine complex solution is 0.5~3h；Reaction
It carries out in a high pressure reaction kettle, reaction temperature is 100~300 DEG C；Reaction time be 1~for 24 hours, so that cupric ammine complex can be filled
Point ground is incorporated on silica/ceramic monolith in the form of being chemically bonded etc., then the copper unbonded by separation, washing removal
Ammino-complex.
In step (6), calcination temperature is 200~800 DEG C；Calcination time is 1~5h；Reducing atmosphere is hydrogen and protection
The mixed gas of property gas；Wherein, the protective gas is the combination of one or both of nitrogen, helium or argon gas；Institute
It states in mixed gas, the volume fraction of hydrogen is 10~100%；The temperature of reduction activation is 200~600 DEG C；When reduction activation
Between be 1~6h.
As another aspect of the present invention, additionally provide using copper-carbon/dioxy made from preparation method as described above
SiClx integral catalyzer, wherein the copper-based load capacity relative to silica is 0.5~40wt%, carbon phase is for silica
Load capacity be 0.1~10%, surplus is carrier.
Below in conjunction with specific embodiment, to copper-carbon/silica/ceramic monolith catalyst of the invention and its preparation
Method is described in further detail.
Embodiment 1
(1) cordierite ceramic is put into 10wt%HNO3After middle ultrasound about 2~3h, dry 12h at 120 DEG C；
(2) by step (1) is resulting calcine 2h at 500 DEG C in Muffle furnace by pretreated cordierite ceramic after by institute
It obtains cordierite ceramic and immerses 30min in 30wt% silica solution, extra silica solution is gently blown away with compressed air；By what is impregnated
Cordierite ceramic dry 12h at 100 DEG C；
(3) step (2) are repeated several times until SiO2Overlay capacity is 0.1mg~2mg (SiO2)/mm3(ceramics)；
(4) at room temperature, respectively by 12g Cu (NO3)2·3H2O and 4.4g NaOH is dissolved in the deionized water of equivalent, stirring
Two kinds of solution are mixed under state, obtain metal hydroxides suspension；
(5) 10g trimesic acid is dissolved in ethyl alcohol, it is mixed with step (4) acquired solution under stirring and
Ultrasound 3h at 40 DEG C；
(6) mixed solution obtained by step (5) is subjected to washing and separates to obtain solid composite when being 6~7 to pH；By gained
Solid composite is scattered in the deionized water of 400mL, adjusts pH to 11 using ammonium hydroxide under stirring；
(7) SiO for obtaining step (3)2/ carrier cordierite ceramic immerses 30min in step (6) acquired solution；
(8) solidliquid mixture in step (7) is transferred in the autoclave of polytetrafluoroethylsubstrate substrate at 140 DEG C instead
12h is answered, is 7 by separation of solid and liquid and washing to pH value, obtains solid composite；
(9) 4h will be calcined at solid composite that step (8) obtains in air 400 DEG C, then in H2With N2Mixing
In gas (volume fraction of H2 is 10%), reduction activation 4h at 350 DEG C obtains copper-carbon/silica/ceramic monolith and urges
Agent.
SEM characterization
Resulting copper-carbon/the silica of the present embodiment/ceramic monolith catalyst is subjected to SEM characterization, as a result such as Fig. 1
Shown, cordierite ceramic wall thickness increases 0.15mm；It is urged by copper-carbon/silica/ceramic monolith prepared by the method
Copper-carbon/silica can be successfully loaded to cordierite ceramic and obtain the integral catalyzer of easy industrial application by agent.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of copper-carbon/silica/ceramic monolith catalyst preparation method, which is characterized in that the preparation method packet
Include following steps:
(1) nonloaded silica obtains silica/ceramic monolith on ceramic monolith；
(2) copper salt solution and strong base solution are mixed to get copper hydroxide suspension；
(3) trimesic acid solution is mixed with the copper hydroxide suspension, ultrasound, by the mixed liquor solid-liquid after ultrasound point
From；
(4) it is dispersed in water after washing step (3) separating obtained solid to neutrality, adjusting pH value using weak base is 10~13,
Obtain cupric ammine complex solution；
(5) silica for obtaining step (1)/ceramic monolith immerses in the cupric ammine complex solution, adds in heating
It is reacted under the conditions of pressure, obtains solid composite after separating, washing to neutrality；
(6) solid composite for obtaining step (5) is calcined, and then reduction activation in reducing atmosphere, obtains copper-
Carbon/silica/ceramic monolith catalyst.
2. preparation method according to claim 1, which is characterized in that step (1) includes following sub-step:
Sub-step (1a): dry after ceramic monolith is ultrasonically treated in acid solution；
Sub-step (1b): it after sonicated ceramic monolith is calcined, is dipped in silicon source solution for a period of time, is blown with gas
Sweep redundant solution and drying；
Sub-step (1c): repeat sub-step (1b) to load capacity of the silica on the ceramic monolith reach 0.1mg~
2mg/mm3After be dried, calcine.
3. preparation method according to claim 2, it is characterised in that:
In sub-step (1a), the ceramic monolith is one of cordierite ceramic, zirconia ceramics and aluminium oxide ceramics or two
Kind or more combination；The acid solution is nitric acid and/or sulfuric acid solution, and concentration is 5%~30%；Ultrasonic temperature is 20~60
DEG C, the time is 0.5~5h；Drying temperature be 50~150 DEG C, the time be 5~for 24 hours；
In sub-step (1b), calcination temperature is 200~800 DEG C, 1~8h of time；Silicon source is silica solution and/or positive esters of silicon acis；?
Soaking time in the silicon source solution is 0.5~2h；Purge gas is one or more of air, nitrogen and argon gas
Combination；Drying temperature is 80~150 DEG C, the time 2~for 24 hours；
In sub-step (1c), drying temperature is 80~150 DEG C, the time 3~for 24 hours；Calcination temperature is 200~800 DEG C, the time 1~
8h。
4. preparation method according to claim 1, which is characterized in that in step (2), the copper salt solution is by by copper source
It is dissolved in the water and is prepared, copper source is one or more of copper nitrate, copper sulphate, copper chloride and copper acetate
Combination；The strong base solution is prepared by the way that alkali source is dissolved in the water, and the alkali source is sodium hydroxide and/or hydroxide
Potassium.
5. preparation method according to claim 1, which is characterized in that in step (3), the trimesic acid solution passes through
Trimesic acid is dissolved in ethyl alcohol and is prepared；Ultrasonic temperature is 20~60 DEG C, and ultrasonic time is 0.5~6h.
6. preparation method according to claim 1, which is characterized in that in step (4), weak base is ammonium hydroxide or carbonic acid ammonium.
7. preparation method according to claim 1, which is characterized in that in step (5), in the cupric ammine complex solution
Soaking time be 0.5~3h；Reaction carry out in a high pressure reaction kettle, reaction temperature be 100~300 DEG C, the reaction time be 1~
24h。
8. preparation method according to claim 1, which is characterized in that in step (6), calcination temperature is 200~800 DEG C；
Calcination time is 1~5h.
9. preparation method according to claim 1, which is characterized in that in step (6), the reducing atmosphere be hydrogen with
The mixed gas of protective gas；
Wherein, the protective gas is the combination of one or both of nitrogen, helium and argon gas；In the mixed gas,
The volume fraction of hydrogen is 10~100%；
The temperature of reduction activation is 200~600 DEG C；The reduction activation time is 1~6h.
10. copper-carbon/silica/ceramics that a kind of preparation method as described in any one of claims 1 to 9 is prepared are whole
Body formula catalyst, which is characterized in that copper-based relative to silica in the copper-carbon/silica/ceramic monolith catalyst
Load capacity be 0.5~40wt%, carbon phase for silica load capacity be 0.1~10%, surplus is carrier.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357328A (en) * | 2008-09-11 | 2009-02-04 | 南京工业大学 | Fume denitration composite catalyst using titanium-base ceramics as carrier and preparation method thereof |
| CN108816227A (en) * | 2018-05-29 | 2018-11-16 | 中国科学院过程工程研究所 | Derivative carried copper-base catalyst of metal framework and preparation method thereof |
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2018
- 2018-12-29 CN CN201811653477.4A patent/CN109603826B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357328A (en) * | 2008-09-11 | 2009-02-04 | 南京工业大学 | Fume denitration composite catalyst using titanium-base ceramics as carrier and preparation method thereof |
| CN108816227A (en) * | 2018-05-29 | 2018-11-16 | 中国科学院过程工程研究所 | Derivative carried copper-base catalyst of metal framework and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金杏妹: "《工业应用催化剂》", 31 August 2004, 华东理工大学出版社 * |
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