CN103464162A - 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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- CN103464162A CN103464162A CN2013103960982A CN201310396098A CN103464162A CN 103464162 A CN103464162 A CN 103464162A CN 2013103960982 A CN2013103960982 A CN 2013103960982A CN 201310396098 A CN201310396098 A CN 201310396098A CN 103464162 A CN103464162 A CN 103464162A
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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 compound nano-tube array film catalyst, and, as 3-cyano group-3,5 for fixed bed, the 5-trimethylcyclohexanone prepares the purposes of the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
Background technology
3-aminomethyl-3,5,5-trimethyl cyclohexylamine (IPD is called for short IPDA) is the raw material for preparing IPDI (IPDI), polyamide etc.; Also can be used 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
2under the hydrogenation catalyst effect, through ammonification, Hydrogenation, obtain.The cobalt that hydrogenation catalyst commonly used is thunder Buddhist nun cobalt and moulding or ruthenium catalyst.
Thunder Buddhist nun Co catalysts is a business-like catalyst.As U.S. patent document US6087296A, US7569513 etc. disclose its preparation method: take metal Co and Al as alloy bulk, add auxiliary agent Ni, the transition metal such as Mo, Ti, at high temperature melting is the Co-Al alloy, then be broken into alloying pellet, be called catalyst precursor; With certain density NaOH solution, catalyst precursor mesexine Al is taken out to (this step is called activation) and be prepared into thunder Buddhist nun Co catalysts; Then will activate with distilled water the thunder Buddhist nun Co catalysts prepared cleans to scrub raffinate pH=7～8.Preparation the type catalyst disadvantage is to produce a large amount of alkalescence containing the heavy metal waste liquid in cleaning thunder Buddhist nun Co catalysts process, generally prepares 1t thunder Buddhist nun Co catalysts and produces about 30t waste water.
U.S. patent document US2003120115A1, US6790996B2, Chinese patent document CN1561260A discloses the preparation method of cobalt or the ruthenium catalyst of moulding: 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 that cobalt or ruthenium are deposited on to 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; Use H during use
2cobalt oxide or ruthenium-oxide are reduced into to 0 valency cobalt or ruthenium.The catalyst of this moulding is easily efflorescence in use, and blocking pipe or valve make production be difficult to run well; The catalyst activity component easily runs off, and activity and selectivity descends; The active component run off enters in product, and separation difficulty, affect product quality.US6337300B1, US6486366, US6573213, U.S.'s patent documents such as US6649799 are also mentioned with Co-Al alloyed powder moulding or by it and are coated with stain on the polystyrene sphere surface, and then activate with alkali lye, distilled water cleans and to obtain catalyst, this alloyed powder moulding reactivation is made to the shortcoming that catalyst has the first two method concurrently.Therefore, need to find a kind of environmental protection, high, the selective height of catalyst activity that prepare and stablize durable method.
Anodic oxidation is the electrochemical oxidation of metal or alloy, has at present lot of documents to be reported in the electrolyte of fluoride ion and adopts the method to prepare caliber from several nanometers to several microns at Ti and alloy surface thereof, and pipe range reaches the nano-tube array of 1mm left and right.Nano-tube array aperture homogeneous prepared by the method, tube wall is smooth, and nanotube aperture and pipe range are 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
3compound nano-tube array film catalyst have not been reported for the preparation of the 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 compound nano-tube array film catalyst.The method can not produce a large amount of waste water, and the catalyst aperture homogeneous prepared, and tube wall is smooth, and pipe range is controlled, and the duct direction is consistent.
Another object of the present invention is to provide Co and Al
2o
3compound nano-tube array film catalyst is as with 3-cyano group-3,5, and the 5-trimethylcyclohexanone is the purposes that raw material prepares the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
For reaching above purpose, technical scheme of the present invention is as follows:
A kind of Co and Al
2o
3the preparation method of compound nano-tube array film catalyst comprises:
(1), melting prepares the Co-Al alloy sheet;
(2), the Co-Al alloy sheet of preparation in step (1) of take is anode, carry out the constant voltage anodic oxidation and prepare superficial growth CoO and Al are arranged in electrolyte
2o
3the alloy sheet of composite nano tube array films, then use the electrolyte of distilled water flushing alloy sheet surface attachment;
(3), the superficial growth made in step (2) is had to 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 to H at a certain temperature
2reduction obtains Co and Al
2o
3compound nano-tube array film catalyst.
As a kind of preferred technical scheme, preparation method of the present invention comprises following concrete steps:
(1), melting Co-Al alloy sheet: wherein, the weight based on Co and Al and, the consumption of Co is 20～30wt%, the consumption of Al is 70～80wt%; Can optionally 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
3compound film of Nano tube array: the Co-Al alloy sheet that the step (1) of take makes is anode, a kind of in the conductive material of the electrolyte resistances such as high purity graphite, platinum and ruthenium corrosion of take is negative electrode, adjust distance between negative electrode and anode, in containing the electrolyte of urea, the constant voltage anodic oxidation obtains superficial growth CoO and Al
2o
3the alloy sheet of compound film of Nano tube array, then with the electrolyte of this alloy sheet surface attachment of distilled water flushing;
(3) superficial growth, (2) made has CoO and Al
2o
3the alloy sheet of compound film of Nano tube array is broken into the alloying pellet that equivalent diameter is 2～3.8mm, is catalyst precursor;
(4), catalyst precursor that (3) are made under 300～500 ℃, use H
2reduction 3～5hr, obtain Co and Al
2o
3compound nano-tube array film catalyst.
In method of the present invention, in step 1), the addition of auxiliary agent be relative Co and Al weight and 0～2wt%, preferred 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 for adding the organic solvent of 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%, and preferred 1～4v%, based on the electrolyte cumulative volume; In electrolyte, electrolytical concentration is 0.05～5wt%, and preferred 0.5～2wt%, based on the electrolyte gross weight.
In method of the present invention, step 2) in, the anodised voltage of constant voltage is 10～80V, preferably 20～35V; The 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 is 1:1～1:2 with the cathode area ratio, preferably 1:1.3～1:1.6.
In method of the present invention, the urea in the electrolyte in step (2) is to add as nanotube intensity and growth promoter in batches, and in the total addition of urea and electrolyte, the mol ratio of distilled water is 1:1～1:2.Urea add method and the mechanism of action as follows:
At first, the formation mechanism of nanotube is: nanotube forms mechanism can divide three steps (Fig. 1 is shown in by schematic diagram), the first step: quick active dissolution post-passivation occurs in metal or its alloy surface, forms 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 that anode is contained, and n represents that this metal forms the valence state of oxide); Second step, the integrality of passivating film is at electric field, H
+with under the F-effect, destroyed, form nanotube blank (original embryo hole); The 3rd step: H
+, F
-deng the oxide-film (field-enhanced dissolution) at place, etching embryo hole under the assistance of electric field force, vertically etching forms deep hole, and nanotube starts growth, until the nanotube surface dissolution velocity is greater than the fltting speed of nanotube to matrix; Lateral etching, it is large that the aperture of nanotube becomes, the tube wall attenuation, 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
+constantly form, then move along nanotube from established nanotube bottom, finally in electrolyte.H
+, F
-deng corroding nanotube walls and the nanotube surface formed under the effect of the assistance at electric field force, cause nanotube strength decreased and nanotube growth speed (nanotube growth speed=nanotube is to matrix fltting speed-nanotube surface dissolution velocity) to slow down.
The mode that adds of urea is: after 5～10min is carried out in anodic oxidation, add first urea, account for the 10～20wt% that adds the urea total amount, after 2～2.5hr is carried out in anodic oxidation, every 30～60min, the urea of surplus is added in batches to every crowd of 5～10wt% that addition is the urea total amount.In the anodic oxidation incipient stage, i.e. front 5～10min left and right that anodic oxidation is carried out, belong to passivating film and embryo hole and form the stage, and the formation stages in embryo hole needs H
+effect (selective corrosion), if add urea will be unfavorable for the formation in embryo hole in the embryo hole formation stage.Start to enter the nanotube growth stage after anodic oxidation 5～10min (anodic oxidation 5～10min is to anode oxidation 2～2.5hr), this one-phase nanotube is greater than the nanotube surface dissolution velocity to the matrix fltting speed, i.e. H in electrolyte
+concentration is not very high, do not need too many hydrolysis of urea go in and electrolyte in H
+, add the urea of 10～20wt% just can eliminate a part of H in electrolyte in during this period of time
+, reduce H
+enrichment speed in electrolyte, slow down anodic oxidation and enter equilibrium stage (nanotube equates with the nanotube surface dissolution velocity to the matrix fltting speed), is conducive to the nanotube Fast Growth.After anodic oxidation 2～2.5hr, H in electrolyte now
+the concentration maximum, nanotube is close with nanotube surface dissolution velocity size to the matrix fltting speed, in equilibrium stage, can add every 30～60min 5～10% urea, the NH that now hydrolysis of urea produces
3eliminate a part of H
+, reduce the nanotube surface dissolution velocity, be conducive to the nanotube continued growth, can also improve the integrality of the nanotube walls prepared; So not only be conducive to the nanotube Fast Growth but also be conducive to improve the intensity of nanotube; The raising of nanowire growth speed will be shortened electrolysis time, reduce energy consumption; Improve nano-tube array intensity and will reduce that its structure in catalytic applications is caved in and the risk of loss of active component, extend the catalyst service life prepared.If every batch adds the too much or disposable urea that will remain all to add in electrolyte, now electrolyte temperature is higher, and urea can be hydrolyzed in a large number, causes on the one hand the pH value increase of electrolyte to cause [MF
6]
(6-n)-hydrolysis becomes metal hydroxides, and these metal hydroxides will be attached to nanotube surface, even enters in nanotube and stops up the nanotube duct, and its catalytic performance is had a negative impact; The NH that hydrolysis produces on the other hand
3measure too large, NH
3in electrolyte, reaching capacity to volatilize away from electrolyte causes environmental pollution, and affects the personnel health.
The catalyst that this method obtains can be used as 3-cyano group-3,5 for fixed bed, and the 5-trimethylcyclohexanone prepares the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
The present invention has the following advantages:
(1), the method can not produce a large amount of waste water, electrolyte used can recycle, the step of unique generation waste water is CoO and the Al that anodic oxidation obtains
2o
3compound film of Nano tube array needs a small amount of distilled water flushing; As calculated, the 1t product expends about 2.4t distilled water, correspondingly only produces about 2.4t waste water;
(2), CoO and the Al of preparation
2o
3compound film of Nano tube array fast growth, intensity are high: the speed of growth of nanotube is increased to 1.45 μ m/hr by the approximately 0.76 μ m/hr that does not add urea, by scratching instrument (the WS-92 type acoustic emission scratching instrument test of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences) test nano-tube array film-strength, by the 2.8N that does not add urea, is increased to 20.4～24N; The Co finally obtained and Al
2o
3compound nano-tube array film-strength is high, does not in use occur that structure is caved in and the loss of active component phenomenon.
(3), the catalyst aperture homogeneous for preparing of the method, tube wall is smooth, caliber and pipe range are controlled, and the duct direction is consistent, have the characteristics of shape-selective catalyst, show selective (reaching more than 98%) very high to IPDA.
The accompanying drawing explanation
Fig. 1 is that film of Nano tube array forms the mechanism sketch;
Fig. 2 is that anodic oxidation prepares CoO and Al
2o
3compound nano-tube array film device schematic diagram.Wherein, " 1 " is D.C. regulated power supply; " 2 " are negative electrode; " 3 " are Co-Al alloy sheet anode.
The specific embodiment
For a better understanding of the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention not only is confined to the following examples.
In the embodiment of the present invention, D.C. regulated power supply used is that Yangzhou Shuanghong Electronics Co., Ltd. produces.
In the embodiment of the present invention, scratching instrument used adopts the WS-92 type acoustic 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 produced for Micromeritics Instrument Corp. U.S.A, and model is ASAP2020.
Weighing 100g cobalt, 400g aluminium, add these metals in the furnace chamber of intermediate frequency furnace (being purchased from the Suzhou rich vacuum technology of perseverance Co., Ltd), and 1600 ℃ 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
4f, the 3200g ethylene glycol solution of 2.8v% distilled water, as electrolyte, adopts device as shown in Figure 2; Urea is added in electrolyte, the distilled water mol ratio in urea total amount and electrolyte is 2:3 in batches, after anodic oxidation 10min, adds first urea, accounts for 10% of total amount, after anodic oxidation 2.5hr, every 30min, adds approximately 8.2% of total amount; Take thickness as 2mm, and size is anode for 8cm * 10cmCo-Al alloy sheet, and high purity graphite is negative electrode, and anode is with cathode area than being 1:1.3, and distance between the two is set as 3.5cm, constant voltage anodic oxidation 8hr under 25V voltage, and making superficial growth has CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array reaches 22.7N); Then it is broken into to alloying pellet, is catalyst precursor; Get the 70ml catalyst precursor and pack in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it under 300 ℃, and then obtains Co and Al at 400 ℃ of lower reduction activation 2hr
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent, move continuously 110hr, the IPN conversion ratio reaches 100%, to IPDA selectively be up to 94.7%, on average reach 94.2%.Collect product and carry out the ICP-OES analysis, do not find metal promoter and active component Co; Specific area and pore structure that BET analyzes the discovery catalyst all do not have to change before and after estimating, and illustrate that estimating this catalyst of front and back the efflorescence leakage do not occur.
Weighing 125g cobalt, 370g aluminium, 2g nickel, 2g chromium, add these metals in the furnace chamber of intermediate frequency furnace (being purchased from the Suzhou rich vacuum technology of perseverance Co., Ltd) 1600 ℃ of heat fused, 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
4f, the ethylene glycol solution 3240g of 2.8v% distilled water, as electrolyte, adopts device as shown in Figure 2; Urea is added in electrolyte, the distilled water mol ratio in urea total amount and electrolyte is 1:2 in batches, after anodic oxidation 5min, adds first urea, accounts for 12% of total amount, after anodic oxidation 2hr, every 30min, adds 8% of total amount; Take thickness as 2mm, and size is anode for 8cm * 10cmCo-Al alloy sheet, and platinum is negative electrode, and anode is with cathode area than being 1:1.3, and distance between the two is set as 3.5cm, constant voltage anodic oxidation 7.5hr under 20V voltage, and making surface has CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array reaches 20.4N); Then it is broken into to alloying pellet, is catalyst precursor; Get the 70ml catalyst precursor and pack in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it under 300 ℃, and then obtains Co and Al at 400 ℃ of lower reduction activation 2hr
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent, move continuously 124hr, the IPN conversion ratio reaches 100%, to IPDA selectively be up to 98.7%, on average reach 97.8%.Collect product and carry out the ICP-OES analysis, do not find metal promoter and active component Co; Specific area and pore structure that BET analyzes the discovery catalyst all do not have to change before and after estimating, and illustrate that estimating this catalyst of front and back the efflorescence leakage do not occur.
Weighing 100g cobalt, 394g aluminium, 3g molybdenum, 3g iron, add these metals in the furnace chamber of intermediate frequency furnace (being purchased from the Suzhou rich vacuum technology of perseverance Co., Ltd) 1600 ℃ of heat fused, pour in 8cm * 10cm mould, the Co-Al alloy sheet that thickness is about 2mm is made in melting in batches.
Preparation is containing 0.5wt%NaF, and the diethylene glycol solution 3600g of 1.5v% distilled water, as electrolyte, adopts device as shown in Figure 2; Urea is added in electrolyte, the distilled water mol ratio in urea total amount and electrolyte is 3:4 in batches, after anodic oxidation 8min, adds first urea, accounts for 20% of total amount, after anodic oxidation 2hr, every 30min, approximately adds 8.9% of total amount; Take thickness as 2mm, and size is anode for 8cm * 10cmCo-Al alloy sheet, and ruthenium is negative electrode, and anode is with cathode area than being 1:1.5, and distance between the two is set as 4.5cm, constant voltage anodic oxidation 6.5hr under 30V voltage, and making surface has CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array reaches 23.8N); Then it is broken into to alloying pellet, is catalyst precursor; Get the 70ml catalyst precursor and pack in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it under 300 ℃, and then obtains Co and Al at 400 ℃ of lower reduction activation 2hr
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent and estimate, move continuously 128hr, the IPN conversion ratio reaches 100%, to IPDA selectively be up to 98.4%, on average reach 97.2%.Collect product and carry out the ICP-OES analysis, do not find metal promoter and active component Co; Specific area and pore structure that BET analyzes the discovery catalyst all do not have to change before and after estimating, and illustrate that estimating this catalyst of front and back the efflorescence leakage do not occur.
Embodiment 4
Weighing 140g cobalt, 347.5g aluminium, 5g titanium, the 2g ruthenium, add these metals in the furnace chamber of intermediate frequency furnace (being purchased from the Suzhou rich vacuum technology of perseverance Co., Ltd) 1600 ℃ of heat fused, pour in 8cm * 10cm mould, the Co-Al alloy sheet that thickness is about 2mm is made in melting in batches.
Preparation is containing 2wt%KF, and the glycerine solution 3860g of 4v% distilled water, as electrolyte, adopts device as shown in Figure 2; Urea is added in electrolyte, the distilled water mol ratio in urea total amount and electrolyte is 1:1 in batches, after anodic oxidation 10min, adds first urea, accounts for 10% of total amount, after anodic oxidation 2hr, every 30min, adds 9% of total amount; Take thickness as 2mm, and size is anode for 8cm * 10cmCo-Al alloy sheet, and high purity graphite is negative electrode, and anode is with cathode area than being 1:1.5, and distance between the two is set as 5cm, constant voltage anodic oxidation 7hr under 25V voltage, and making surface has CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array reaches 22.7N); Then it is broken into to alloying pellet, is catalyst precursor; Get the 70ml catalyst precursor and pack in fixed bed reactors, use N
2/ H
2gaseous mixture (both volume ratio 2:1) first carries out reduction activation 2hr to it under 300 ℃, and then obtains Co and Al at 400 ℃ of lower reduction activation 2hr
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent and estimate, move continuously 128hr, the IPN conversion ratio reaches 100%, to IPDA selectively be up to 98.2%, on average reach 97.1%.Collect product and carry out the ICP-OES analysis, do not find metal promoter and active component Co, specific area and pore structure that BET analyzes the discovery catalyst all do not have to change before and after estimating, and illustrate that estimating this catalyst of front and back the efflorescence leakage do not occur.
Comparative Examples 1
Formula and method melting by embodiment 1 prepare alloy sheet; In anode oxidation process, except not adding in electrolyte urea, other anodic oxidation condition is fully identical with embodiment 1, and anodic oxidation makes surface CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array is only 3.4N); Employing obtains Co and Al with the method reduction of embodiment 1
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent, move continuously 86hr, the IPN conversion ratio reaches 98.6%, to IPDA selectively be up to 96.9%, on average reach 95.8%.Collect product and carry out the ICP-OES analysis, the Co of 387ppm is arranged in product; BET analyze to find that the specific area of catalyst estimates front reduction approximately 67.6%, illustrates that in the catalyst use procedure, structure is caved in, and the efflorescence leakage is arranged.
Comparative Examples 2
Formula and method melting by embodiment 1 prepare alloy sheet; In anode oxidation process, do not adopt the method that in batches adds urea, but when preparation electrolyte, urea is all added, other anodic oxidation condition is fully identical with embodiment 1, and anodic oxidation makes surface CoO and Al
2o
3the alloy sheet of compound film of Nano tube array (intensity of scratching instrument test film of Nano tube array is 18.1N); Employing obtains Co and Al with the method reduction of embodiment 1
2o
3compound nano-tube array film catalyst.
Carry out IPN Hydrogenation IPDA performance evaluation with reference to 9 pairs of these catalyst of embodiment in the CN101386579A patent, move continuously 68hr, the IPN conversion ratio reaches 92.6%, to IPDA selectively be up to 89.9%, on average reach 88.8%.Collect product and carry out the ICP-OES analysis, do not find metal promoter and active component Co, BET analyzes specific area and the pore structure of finding catalyst all not to be had to change before and after estimating, but compare the specific area of the catalyst that embodiment 1 makes, this Comparative Examples makes specific surface area of catalyst and is about the former 69.3%.The little catalyst treatment ability that causes of specific area is low, and the conversion ratio of IPN descends.
Claims (11)
1. a Co and Al
2o
3the preparation method of compound nano-tube array film catalyst, is characterized in that, described method comprises:
(1), melting prepares the Co-Al alloy sheet;
(2), the Co-Al alloy sheet of preparation in step (1) of take is anode, carry out the constant voltage anodic oxidation and prepare superficial growth CoO and Al are arranged in electrolyte
2o
3the alloy sheet of composite nano tube array films, then use the electrolyte of distilled water flushing alloy sheet surface attachment;
(3), the superficial growth made in step (2) is had to CoO and Al
2o
3the alloy sheet of composite nano tube array films is broken into alloying pellet, is catalyst precursor;
(4), by the catalyst precursor H obtained in step (3)
2reduction obtains Co and Al
2o
3compound nano-tube array film catalyst.
2. the method for claim 1, is characterized in that, during melting Co-Al alloy sheet, the addition of Co is 20～30wt% in step (1), and the addition of Al is 70%～80wt%, the weight based on Co and Al and.
3. method as claimed in claim 1 or 2, it is characterized in that, during the middle melting Co-Al alloy sheet of step (1), optionally add one or two 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 0～2wt%, preferred 0.8～1.4wt%.
4. the method for claim 1, is characterized in that, in step (2), cathode material is selected from a kind of in high purity graphite, platinum and ruthenium.
5. the method for claim 1, is characterized in that, the solvent of preparation electrolyte is for adding the organic solvent of 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%, preferred 1～4v%, the cumulative volume based on electrolyte.
6. method as described as claim 1 or 5, is characterized in that, the electrolyte in step (2) in electrolyte is selected from NaF, KF and NH
4one or two or more in F, in electrolyte, electrolytical concentration is 0.05～5wt%, preferred 0.5～2wt%, based on the electrolyte weight meter.
7. 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.
8. method as claimed in claim 7, it is characterized in that, the method that adds 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 in batches to every crowd of 5～10wt% that addition is the urea total amount every 30～60min.
9. the method for claim 1, is characterized in that, the anodised voltage of constant voltage is 10～80V, preferably 20～35V; The 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 is 1:1～1:2 with the cathode area ratio, preferably 1:1.3～1:1.6.
10. the method for claim 1, is characterized in that, in step (4), reduction temperature is 300～500 ℃, and the recovery time is 3～5hr.
11. the catalyst that a preparation method as described as any one in claim 1-10 obtains is as with 3-cyano group-3,5, the 5-trimethylcyclohexanone is the purposes that raw material prepares the hydrogenation catalyst of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
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