CN103464162B - Preparation method and application of Co and Al2O3 compound nanotube array membrane catalyst - Google Patents
Preparation method and application of Co and Al2O3 compound nanotube array membrane catalyst Download PDFInfo
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- CN103464162B CN103464162B CN201310396098.2A CN201310396098A CN103464162B CN 103464162 B CN103464162 B CN 103464162B CN 201310396098 A CN201310396098 A CN 201310396098A CN 103464162 B CN103464162 B CN 103464162B
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Abstract
The invention discloses a preparation method and application of a Co and Al2O3 compound nanotube array membrane catalyst. The method comprises the following steps of: carrying out constant-pressure anodic oxidation in a urea-containing electrolyte by taking a Co-Al alloy sheet as an anode and high-purity graphite or an other conducting material as a cathode to prepare an alloy sheet with a Co and Al2O3 compound nanotube array membrane grown on a surface; then crushing the obtained alloy sheet into alloy granules, namely catalyst precursors; reducing the catalyst precursors by using H2 to obtain the Co and Al2O3 compound nanotube array membrane catalyst with uniform apertures, smooth tube walls, controllable pipe lengths and consistent pore path directions. The novel catalyst disclosed by the invention is used for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine (IPDA) by carrying out catalytic hydrogenation on 3-cyano-3,5,5-trimethyl cyclohexanone (IPN) and can achieve the maximal transformation rate of IPN by 100% and achieve the maximal selectivity of IPDA more than 98%.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of catalyst, specifically a kind of Co and Al
2o
3the preparation method of the nano-tube array film catalyst of compound, and the purposes preparing the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine as fixed bed with 3-cyano group-3,5,5-trimethylcyclohexanone.
Background technology
3-aminomethyl-3,5,5-trimethyl cyclohexylamine (IPD is called for short IPDA) is the raw material preparing IPDI (IPDI), polyamide etc.; Also can as epoxy curing agent.It is usually by 3-cyano group-3,5,5-trimethylcyclohexanone (cyan-3,5,5-trimethyl cyclohexanone is called for short IPN), NH
3and H
2obtain through ammonification, Hydrogenation under hydrogenation catalyst effect.Conventional hydrogenation catalyst is thunder Buddhist nun cobalt and shaping cobalt or ruthenium catalyst.
Thunder Buddhist nun Co catalysts is a business-like catalyst.As US publication document US6087296A, US7569513 etc. disclose its preparation method: with metal Co and Al for alloy bulk, and add the transition metal such as auxiliary agent Ni, Mo, Ti, at high temperature melting is Co-Al alloy, then be broken into alloying pellet, be called catalyst precursor; Catalyst precursor mesexine Al taken out (this step is called activation) by certain density NaOH solution and be prepared into thunder Buddhist nun Co catalysts; Then clean to scrub raffinate pH=7 ~ 8 with the thunder Buddhist nun Co catalysts of distilled water by activation preparation.Preparation the type catalyst disadvantage produces a large amount of alkalescence containing heavy metal waste liquid in cleaning thunder Buddhist nun Co catalysts process, and general preparation 1t thunder Buddhist nun Co catalysts produces about 30t waste water.
US publication document US2003120115A1, US6790996B2, Chinese patent document CN1561260A discloses shaping cobalt or the preparation method of ruthenium catalyst: in cobalt salt or ruthenium salting liquid (generally also can add the transition metal salt solution such as a certain amount of Ni, Fe), add carbonate or alkali cobalt or ruthenium are deposited on Al with cobalt carbonate or carbonic acid ruthenium or cobalt hydroxide or hydroxide ruthenium form
2o
3, SiO
2, TiO
2with the carrier surface such as Si-Al molecular sieve, carry out drying, then pulverize, add the extrusion moldings such as binding agent, then roasting becomes catalyst precursor; H during use
2cobalt oxide or ruthenium-oxide are reduced into 0 valency cobalt or ruthenium.This shaping catalyst is easily efflorescence in use, blocking pipe or valve, makes production be difficult to run well; Catalyst activity component easily runs off, and activity and selectivity declines; The active component run off enters in product, and separation difficulty, affects product quality.US6337300B1, US6486366, US6573213, the US publication documents such as US6649799 are also mentioned shaping with Co-Al alloyed powder or are coated with stain on polystyrene sphere surface, and then activate with alkali lye, distilled water cleaning obtains catalyst, this shaping for alloyed powder reactivation is obtained the shortcoming that catalyst has first two method concurrently.Therefore, need high, the selective height of catalyst activity that find a kind of environmental protection, that prepare and stablize durable method.
The electrochemical oxidation of anodic oxidation and metal or alloy, have lot of documents to be reported in the electrolyte of fluoride ion at present and adopt the method to prepare caliber from a few nanometer to several microns at Ti and alloy surface thereof, pipe range reaches the nano-tube array of about 1mm.Nano-tube array aperture prepared by the method is homogeneous, and tube wall is smooth, nanotube aperture and pipe range controlled; But the nanotube intensity of preparation is low at present, poor growth (preparing the anodizing time length that longer nanotube needs).And adopt anodizing to prepare Co and Al
2o
3the nano-tube array film catalyst of compound have not been reported for the preparation of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
Summary of the invention
One object of the present invention is to provide a kind of Co and Al
2o
3the preparation method of the nano-tube array film catalyst of compound.The method can not produce a large amount of waste water, and the catalyst aperture prepared is homogeneous, and tube wall is smooth, and pipe range is controlled, and direction, duct is consistent.
Another object of the present invention is to provide Co and Al
2o
3the nano-tube array film catalyst of compound is as being the purposes that the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine prepared by raw material with 3-cyano group-3,5,5-trimethylcyclohexanone.
For reaching above object, technical scheme of the present invention is as follows:
A kind of Co and Al
2o
3the preparation method of the nano-tube array film catalyst of compound comprises:
(1), Co-Al alloy sheet is prepared in melting;
(2), with the Co-Al alloy sheet of preparation in step (1) for anode, carry out constant voltage anodic oxidation in the electrolytic solution and prepare superficial growth and have CoO and Al
2o
3the alloy sheet of composite nano tube array films, then uses the electrolyte of distilled water flushing alloy sheet surface attachment;
(3), superficial growth obtained in step (2) there is CoO and Al
2o
3the alloy sheet of composite nano tube array films is broken into the alloying pellet of certain size, is catalyst precursor;
(4), the catalyst precursor obtained in step (3) is used H at a certain temperature
2reduction obtains Co and Al
2o
3the nano-tube array film catalyst of compound.
As the preferred technical scheme of one, preparation method of the present invention comprises following concrete steps:
(1), melting Co-Al alloy sheet: wherein, based on Co and Al weight and, the consumption of Co is the consumption of 20 ~ 30wt%, Al is 70 ~ 80wt%; Optionally can add one or two or more in the transition metal such as Ni, Mn, Mo, Fe, Cr, Cu, Ti, Ta, W, Ru and Zr as auxiliary agent;
(2), anodizing prepares CoO and Al
2o
3the film of Nano tube array of compound: the Co-Al alloy sheet obtained with step (1) is for anode, with the one in the conductive material of the electrolyte resistance corrosion such as high purity graphite, platinum and ruthenium for negative electrode, adjustment negative electrode and the spacing of anode, constant voltage anodic oxidation obtains superficial growth in containing the electrolyte of urea CoO and Al
2o
3the alloy sheet of the film of Nano tube array of compound, then with the electrolyte of this alloy sheet surface attachment of distilled water flushing;
(3), the superficial growth that (2) are obtained there is CoO and Al
2o
3the alloy sheet of the film of Nano tube array of compound is broken into the alloying pellet that equivalent diameter is 2 ~ 3.8mm, is catalyst precursor;
(4), by catalyst precursor obtained to (3) at 300 ~ 500 DEG C, H is used
2reduction 3 ~ 5hr, obtains Co and Al
2o
3the nano-tube array film catalyst of compound.
In method of the present invention, in step 1), the addition of auxiliary agent for relative Co and Al weight and 0 ~ 2wt%, preferably 0.8 ~ 1.4wt%.
In method of the present invention, step 2) in, the electrolyte in electrolyte is selected from NaF, KF and NH
4one or two or more in the villiaumite of the easily ionizable in water such as F; The solvent of configuration electrolyte is the organic solvent adding a certain amount of distilled water, organic solvent is selected from the one or two or more in ethylene glycol, diethylene glycol and glycerine, in electrolyte, the addition of distilled water is 0.5 ~ 10v%, preferably 1 ~ 4v%, based on electrolyte cumulative volume; In electrolyte, electrolytical concentration is 0.05 ~ 5wt%, preferably 0.5 ~ 2wt%, based on electrolyte gross weight.
In method of the present invention, step 2) in the anodised voltage of constant voltage be 10 ~ 80V, preferably 20 ~ 35V; Constant voltage anodizing time is 6.3 ~ 20hr, preferably 6.5 ~ 8hr; Distance between negative electrode and anode is 2 ~ 8cm, preferably 3.5 ~ 5cm; Annode area and cathode area are than being 1:1 ~ 1:2, preferred 1:1.3 ~ 1:1.6.
In method of the present invention, in batches the urea in the electrolyte in step (2) add as nanotube intensity and growth promoter, and in the total addition of urea and electrolyte, the mol ratio of distilled water is 1:1 ~ 1:2.Adding Way and the mechanism of action of urea are as follows:
First, the formation mechanism of nanotube is: nanotube formation mechenism can divide three steps (Fig. 1 is shown in by schematic diagram), the first step: metal or its alloy surface generation fast activity dissolve post-passivation, form fine and close passivating film (oxide-film), and the reaction that this step occurs is M+H
2o → MO
n/
2+ H
++ ne
-(M represents the metal contained by anode, and n represents the valence state that this metal forms oxide); Second step, the integrality of passivating film is at electric field, H
+destroyed with under F-effect, formed nanotube blank (primary embryonic hole); 3rd step: H
+, F
-deng the oxide-film (field-enhanced dissolution) etching embryo hole place under the assistance of electric field force, longitudinally etching forms deep hole, and nanotube starts growth, until nanotube surface dissolution velocity is greater than the fltting speed of nanotube to matrix; Lateral etching, the aperture of nanotube becomes large, and tube wall is thinning, and the reaction that this step occurs is MO
n/2+ F
-→ [MF
6]
(6-n)-.In the growth course of nanotube, passivating film constantly advances to matrix, H
+continuous formation, then moves, finally in electrolyte along nanotube bottom established nanotube.H
+, F
-deng the nanotube walls and nanotube surface that have been formed can be corroded under the effect of the assistance of electric field force, the reduction of nanotube intensity and nanotube growth speed (nanotube growth speed=nanotube is to matrix fltting speed-nanotube surface dissolution velocity) is caused to slow down.
The feed postition of urea is: after 5 ~ 10min is carried out in anodic oxidation, add first urea, account for the 10 ~ 20wt% adding urea total amount, after 2 ~ 2.5hr is carried out in anodic oxidation, every 30 ~ 60min, the urea of surplus is added in batches, often criticize 5 ~ 10wt% that addition is urea total amount.In the anodic oxidation incipient stage, i.e. front about 5 ~ 10min of carrying out of anodic oxidation, belong to passivating film and embryo hole formation stages, the formation stages in embryo hole needs H
+effect (selective corrosion), if add at embryo hole formation stages the formation that urea will be unfavorable for embryo hole.Start after anodic oxidation 5 ~ 10min to enter the nanotube growth stage (anodic oxidation 5 ~ 10min is to anodic oxidation 2 ~ 2.5hr), this one-phase nanotube is greater than nanotube surface dissolution velocity to matrix fltting speed, the H namely in electrolyte
+concentration is not very high, the H in not needing too many hydrolysis of urea to go and in electrolyte
+, the urea adding 10 ~ 20wt% during this period of time just can eliminate a part of H in electrolyte
+, reduce H
+enrichment rate in the electrolytic solution, slows down anodic oxidation and enters equilibrium stage (nanotube is equal with nanotube surface dissolution velocity to matrix fltting speed), be conducive to nanotube and grow fast.After anodic oxidation 2 ~ 2.5hr, now H in electrolyte
+concentration is maximum, and nanotube is close with nanotube surface dissolution velocity size to matrix fltting speed, is in equilibrium stage, can add the urea of 5 ~ 10% every 30 ~ 60min, the NH of now hydrolysis of urea generation
3eliminate a part of H
+, reduce nanotube surface dissolution velocity, be conducive to nanotube continued growth, the integrality of the nanotube walls prepared can also be improved; So not only be conducive to the intensity that nanotube grows fast but also is conducive to improving nanotube; The raising of nanowire growth speed will shorten electrolysis time, reduce energy consumption; Improve nano-tube array intensity and will reduce the risk of its structure collapses and loss of active component in catalytic applications, extend the catalyst service life of preparation.If every batch adds and too much or disposablely all to be added in electrolyte by residue urea, now electrolyte temperature is higher, and urea can a large amount of hydrolysis, causes the pH value of electrolyte to increase on the one hand and causes [MF
6]
(6-n)-hydrolysis becomes metal hydroxides, and these metal hydroxides will be attached to nanotube surface, even enter in nanotube and block nanotube duct, have a negative impact to its catalytic performance; The NH of hydrolysis generation on the other hand
3amount is too large, NH
3reaching capacity in the electrolytic solution will volatilize away from electrolyte causes environmental pollution, and affects personnel health.
The catalyst that this method obtains can prepare the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine as fixed bed 3-cyano group-3,5,5-trimethylcyclohexanone.
The present invention has the following advantages:
(1), the method can not produce a large amount of waste water, and electrolyte used can recycle, and unique step producing waste water is CoO and Al that anodic oxidation obtains
2o
3the film of Nano tube array of compound needs a small amount of distilled water flushing; As calculated, 1t product expends about 2.4t distilled water, correspondingly only produces about 2.4t waste water;
(2), CoO and Al of preparation
2o
3the film of Nano tube array fast growth of compound, intensity are high: the speed of growth of nanotube is increased to 1.45 μm/hr by the about 0.76 μm/hr not adding urea, are increased to 20.4 ~ 24N by scratching instrument (the WS-92 type sound emission scratching instrument test of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences) test nano-tube array film-strength by the 2.8N not adding urea; Co and Al finally obtained
2o
3the nano-tube array film-strength of compound is high, does not in use occur structure collapses and loss of active component phenomenon.
(3), the method catalyst aperture of preparing is homogeneous, and tube wall is smooth, caliber and pipe range controlled, and direction, duct is consistent, has the feature of shape-selective catalyst, shows selective (reaching more than 98%) very high to IPDA.
Accompanying drawing explanation
Fig. 1 is nano-tube array membrane formation mechanism sketch;
Fig. 2 is that CoO and Al is prepared in anodic oxidation
2o
3the nano-tube array film device schematic diagram of compound.Wherein, " 1 " is D.C. regulated power supply; " 2 " are negative electrode; " 3 " are Co-Al alloy sheet anode.
Detailed description of the invention
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
D.C. regulated power supply used in the embodiment of the present invention is that Yangzhou Shuanghong Electronics Co., Ltd. produces.
Scratching instrument used in the embodiment of the present invention adopts the WS-92 type sound emission scratching instrument test of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences.
Inductive coupling plasma emission spectrograph (ICP-OES) used in the embodiment of the present invention is produced for Agilent Technologies, and model is 720ICP-OES.
Specific surface area analysis instrument (BET) used in the embodiment of the present invention is Micromeritics Instrument Corp. U.S.A's production, and model is ASAP2020.
Embodiment 1
Weigh 100g cobalt, 400g aluminium, added by these metals in the furnace chamber of intermediate frequency furnace (being purchased from Suzhou Heng Fu vacuum technology Co., Ltd), 1600 DEG C of heat fused, pour in 8cm × 10cm mould in batches, and the Co-Al alloy sheet that thickness is about 2mm is made in melting.
Preparation is containing 1wt%NH
4the 3200g ethylene glycol solution of F, 2.8v% distilled water, as electrolyte, adopts device as shown in Figure 2; Add in electrolyte by urea, the distilled water mol ratio in urea total amount and electrolyte is 2:3, after anodic oxidation 10min, adds first urea, accounts for 10% of total amount, after anodic oxidation 2.5hr, add about 8.2% of total amount every 30min in batches; Take thickness as 2mm, size is 8cm × 10cmCo-Al alloy sheet is anode, and high purity graphite is negative electrode, and anode and cathode area are than being 1:1.3, and distance is between the two set as 3.5cm, constant voltage anodic oxidation 8hr under 25V voltage, and obtained superficial growth has CoO and Al
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array reaches 22.7N) of the film of Nano tube array of compound; Then be broken into alloying pellet, be catalyst precursor; Get 70ml catalyst precursor to load in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it at 300 DEG C, and then reduction activation 2hr obtains Co and Al at 400 DEG C
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to embodiment 9 in CN101386579A patent to this catalyst, run 110hr continuously, IPN conversion ratio reaches 100%, is up to 94.7%, on average reaches 94.2% to the selective of IPDA.Collect product and carry out ICP-OES analysis, do not find metal promoter and active component Co; BET analysis finds that the specific area of catalyst and pore structure all do not change before and after evaluation, illustrates that evaluating this catalyst of front and back does not occur efflorescence leakage.
Embodiment 2
Weigh 125g cobalt, 370g aluminium, 2g nickel, these metals are added in the furnace chamber of intermediate frequency furnace (being purchased from Suzhou Heng Fu vacuum technology Co., Ltd), 1600 DEG C of heat fused by 2g chromium, pour in 8cm × 10cm mould, the Co-Al alloy sheet that thickness is about 2mm is made in melting in batches.
Preparation is containing 1.45wt%NH
4the ethylene glycol solution 3240g of F, 2.8v% distilled water, as electrolyte, adopts device as shown in Figure 2; Add in electrolyte by urea, the distilled water mol ratio in urea total amount and electrolyte is 1:2, after anodic oxidation 5min, adds first urea, accounts for 12% of total amount, after anodic oxidation 2hr, add 8% of total amount every 30min in batches; Take thickness as 2mm, size is 8cm × 10cmCo-Al alloy sheet is anode, and platinum is negative electrode, and anode and cathode area are than being 1:1.3, and distance is between the two set as 3.5cm, constant voltage anodic oxidation 7.5hr under 20V voltage, and there is CoO and Al on obtained surface
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array reaches 20.4N) of the film of Nano tube array of compound; Then be broken into alloying pellet, be catalyst precursor; Get 70ml catalyst precursor to load in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it at 300 DEG C, and then reduction activation 2hr obtains Co and Al at 400 DEG C
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to embodiment 9 in CN101386579A patent to this catalyst, run 124hr continuously, IPN conversion ratio reaches 100%, is up to 98.7%, on average reaches 97.8% to the selective of IPDA.Collect product and carry out ICP-OES analysis, do not find metal promoter and active component Co; BET analysis finds that the specific area of catalyst and pore structure all do not change before and after evaluation, illustrates that evaluating this catalyst of front and back does not occur efflorescence leakage.
Embodiment 3
Weigh 100g cobalt, 394g aluminium, 3g molybdenum, these metals are added in the furnace chamber of intermediate frequency furnace (being purchased from Suzhou Heng Fu vacuum technology Co., Ltd), 1600 DEG C of heat fused by 3g iron, pour in 8cm × 10cm mould, the Co-Al alloy sheet that thickness is about 2mm is made in melting in batches.
Preparation contains the diethylene glycol solution 3600g of 0.5wt%NaF, 1.5v% distilled water as electrolyte, adopts device as shown in Figure 2; Add in electrolyte by urea, the distilled water mol ratio in urea total amount and electrolyte is 3:4, after anodic oxidation 8min, adds first urea, accounts for 20% of total amount, after anodic oxidation 2hr, about add 8.9% of total amount every 30min in batches; Take thickness as 2mm, size is 8cm × 10cmCo-Al alloy sheet is anode, and ruthenium is negative electrode, and anode and cathode area are than being 1:1.5, and distance is between the two set as 4.5cm, constant voltage anodic oxidation 6.5hr under 30V voltage, and there is CoO and Al on obtained surface
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array reaches 23.8N) of the film of Nano tube array of compound; Then be broken into alloying pellet, be catalyst precursor; Get 70ml catalyst precursor to load in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it at 300 DEG C, and then reduction activation 2hr obtains Co and Al at 400 DEG C
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA with reference to embodiment 9 in CN101386579A patent to this catalyst to evaluate, run 128hr continuously, IPN conversion ratio reaches 100%, is up to 98.4%, on average reaches 97.2% to the selective of IPDA.Collect product and carry out ICP-OES analysis, do not find metal promoter and active component Co; BET analysis finds that the specific area of catalyst and pore structure all do not change before and after evaluation, illustrates that evaluating this catalyst of front and back does not occur efflorescence leakage.
Embodiment 4
Weigh 140g cobalt, 347.5g aluminium, 5g titanium, these metals are added in the furnace chamber of intermediate frequency furnace (being purchased from Suzhou Heng Fu vacuum technology Co., Ltd), 1600 DEG C of heat fused by 2g ruthenium, pour in 8cm × 10cm mould, the Co-Al alloy sheet that thickness is about 2mm is made in melting in batches.
Preparation contains the glycerin solution 3860g of 2wt%KF, 4v% distilled water as electrolyte, adopts device as shown in Figure 2; Add in electrolyte by urea, the distilled water mol ratio in urea total amount and electrolyte is 1:1, after anodic oxidation 10min, adds first urea, accounts for 10% of total amount, after anodic oxidation 2hr, add 9% of total amount every 30min in batches; Take thickness as 2mm, size is 8cm × 10cmCo-Al alloy sheet is anode, and high purity graphite is negative electrode, and anode and cathode area are than being 1:1.5, and distance is between the two set as 5cm, constant voltage anodic oxidation 7hr under 25V voltage, and there is CoO and Al on obtained surface
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array reaches 22.7N) of the film of Nano tube array of compound; Then be broken into alloying pellet, be catalyst precursor; Get 70ml catalyst precursor to load in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it at 300 DEG C, and then reduction activation 2hr obtains Co and Al at 400 DEG C
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA with reference to embodiment 9 in CN101386579A patent to this catalyst to evaluate, run 128hr continuously, IPN conversion ratio reaches 100%, is up to 98.2%, on average reaches 97.1% to the selective of IPDA.Collect product and carry out ICP-OES analysis, do not find that metal promoter and active component Co, BET analysis find that the specific area of catalyst and pore structure all do not change before and after evaluation, illustrate that evaluating this catalyst of front and back does not occur efflorescence leakage.
Comparative example 1
Alloy sheet is prepared by the formula of embodiment 1 and method melting; In anode oxidation process, except not adding except urea in the electrolytic solution, other anodic oxidation condition is completely identical with embodiment 1, and anodic oxidation obtains surface CoO and Al
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array is only 3.4N) of the film of Nano tube array of compound; The method reduction with embodiment 1 is adopted to obtain Co and Al
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to embodiment 9 in CN101386579A patent to this catalyst, run 86hr continuously, IPN conversion ratio reaches 98.6%, is up to 96.9%, on average reaches 95.8% to the selective of IPDA.Collect product and carry out ICP-OES analysis, in product, have the Co of 387ppm; BET analyzes and finds that the specific area of catalyst reduces about 67.6% before comparatively evaluating, and structure collapses in catalyst use procedure is described, has efflorescence leakage.
Comparative example 2
Alloy sheet is prepared by the formula of embodiment 1 and method melting; In anode oxidation process, do not adopt the method in batches adding urea, but all added by urea when preparing electrolyte, other anodic oxidation condition is completely identical with embodiment 1, and anodic oxidation obtains surface CoO and Al
2o
3the alloy sheet (intensity of scratching instrument test film of Nano tube array is 18.1N) of the film of Nano tube array of compound; The method reduction with embodiment 1 is adopted to obtain Co and Al
2o
3the nano-tube array film catalyst of compound.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to embodiment 9 in CN101386579A patent to this catalyst, run 68hr continuously, IPN conversion ratio reaches 92.6%, is up to 89.9%, on average reaches 88.8% to the selective of IPDA.Collect product and carry out ICP-OES analysis, do not find metal promoter and active component Co, BET analysis finds that the specific area of catalyst and pore structure all do not change before and after evaluation, but compare the specific area of the obtained catalyst of embodiment 1, this comparative example obtain that specific surface area of catalyst is about the former 69.3%.The little catalyst treatment ability that causes of specific area is low, and the conversion ratio of IPN declines.
Claims (15)
1. Co and Al
2o
3the preparation method of the nano-tube array film catalyst of compound, is characterized in that, described method comprises:
(1), Co-Al alloy sheet is prepared in melting;
(2), with the Co-Al alloy sheet of preparation in step (1) for anode, carry out constant voltage anodic oxidation in the electrolytic solution and prepare superficial growth and have CoO and Al
2o
3the alloy sheet of composite nano tube array films, then uses the electrolyte of distilled water flushing alloy sheet surface attachment;
(3), superficial growth obtained in step (2) there is CoO and Al
2o
3the alloy sheet of composite nano tube array films is broken into alloying pellet, is catalyst precursor;
(4) the catalyst precursor H, will obtained in step (3)
2reduction obtains Co and Al
2o
3the nano-tube array film catalyst of compound;
Wherein, the electrolyte in step (2) in electrolyte is selected from NaF, KF and NH
4one or two or more in F.
2. the method for claim 1, is characterized in that, in step (1) during melting Co-Al alloy sheet, the addition of Co is the addition of 20 ~ 30wt%, Al is 70% ~ 80wt%, based on Co and Al weight and.
3. method as claimed in claim 1 or 2, it is characterized in that, in step (1) during melting Co-Al alloy sheet, optionally add one or more in transition metal Ni, Mn, Mo, Fe, Cr, Cu, Ti, Ta, W, Ru and Zr as auxiliary agent, the weight that the addition of auxiliary agent is Co and Al and 0.8 ~ 2wt%.
4. method as claimed in claim 3, is characterized in that, the weight that the addition of auxiliary agent is Co and Al and 0.8 ~ 1.4wt%.
5. the method for claim 1, is characterized in that, in step (2), cathode material is selected from the one in high purity graphite, platinum and ruthenium.
6. the method for claim 1, is characterized in that, the solvent of preparation electrolyte is the organic solvent adding distilled water, and described organic solvent is selected from the one or two or more in ethylene glycol, diethylene glycol and glycerine; In electrolyte, the addition of distilled water is 0.5 ~ 10v%, based on the cumulative volume of electrolyte.
7. method as claimed in claim 6, it is characterized in that, in electrolyte, the addition of distilled water is 1 ~ 4v%, based on the cumulative volume of electrolyte.
8. the method as described in claim 1 or 6, is characterized in that, in step (2), in electrolyte, electrolytical concentration is 0.05 ~ 5wt%, based on electrolyte weight meter.
9. method as claimed in claim 8, is characterized in that, in electrolyte, electrolytical concentration is preferred 0.5 ~ 2wt%, based on electrolyte weight meter.
10. the method for claim 1, is characterized in that, in the anode oxidation process of step (2), in electrolyte, adds urea in batches, and in the urea total amount added and electrolyte, the mol ratio of distilled water is 1:1 ~ 1:2.
11. methods as claimed in claim 10, it is characterized in that, the Adding Way of urea is: after 5 ~ 10min is carried out in anodic oxidation, add first urea, account for 10 ~ 20wt% of added urea total amount, after 2 ~ 2.5hr is carried out in anodic oxidation, the urea of surplus is added every 30 ~ 60min in batches, often criticize 5 ~ 10wt% that addition is urea total amount.
12. the method for claim 1, is characterized in that, the anodised voltage of constant voltage is 10 ~ 80V; Constant voltage anodizing time is 6.3 ~ 20hr; Distance between negative electrode and anode is 2 ~ 8cm; Annode area and cathode area are than being 1:1 ~ 1:2.
13. methods as claimed in claim 12, it is characterized in that, the anodised voltage of constant voltage is 20 ~ 35V; Constant voltage anodizing time is 6.5 ~ 8hr; Distance between negative electrode and anode is 3.5 ~ 5cm; Annode area and cathode area are than being 1:1.3 ~ 1:1.6.
14. the method for claim 1, is characterized in that, in step (4), reduction temperature is 300 ~ 500 DEG C, and the recovery time is 3 ~ 5hr.
The catalyst that 15. 1 kinds of preparation methods according to any one of claim 1-14 obtain is as being the purposes that the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine prepared by raw material with 3-cyano group-3,5,5-trimethylcyclohexanone.
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