CN103055939B - Preparation method for porous biomimetic catalytic material and application thereof - Google Patents
Preparation method for porous biomimetic catalytic material and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method for a porous biomimetic catalytic material and application thereof. The preparation method comprises the following steps of dissolving chitosan into acetic acid solution, stirring and dropwise adding ammonia water until the pH value is between 6.5 and 7; adding 4-(p-carboxy phenyl) metalloporphyrin ethanol solution, stirring for 24 h, and then adding NH4HCO3 solution, and uniformly stirring; drying by an infrared lamp, and performing vacuum drying to obtain the porous biomimetic catalytic material. The porous biomimetic catalytic material comprises the following components in part by weight 17.6 parts of chitosan, 8.78 parts of glacial acetic acid, 0.0878 part of ammonia water, 0.0176 part of metalloporphyrin, 43.9 parts of ammonium bicarbonate, 500 parts of distilled water and 100 parts of ethanol. Compared with the metalloporphyrin homogeneous catalytic material, the porous biomimetic catalytic material has the advantages that the metalloporphyrin is less in using amount and lower in cost and is easier to separate. The porous biomimetic catalytic material can obviously improve the one-way conversion rate of cyclohexane and the yield of main products and can be reused at least seven times, the average conversion rate of the cyclohexane is between 15.2 and 17.0 percent, and the average conversion rate of ketone alcohol is between 10.9 and 12.7 percent.
Description
Technical field
The invention belongs to technical field of chemical engineering, the preparation method and application that relate to a kind of porous type bionic catalysis material, specifically, by four (to carboxyl phenyl) metalloporphyrin, by acid-base reaction and coordination, be bonded in the Measurement of Biopolymer Chitosan (CTS) with porous and prepare porous type bionic catalysis material.And this type of material is applied to selective catalysis air oxidation of cyclohexane production cyclohexanone and cyclohexanol.
Background technology
The two mixture of cyclohexanone and cyclohexanol is commonly called as KA oil, can prepare caprolactam and adipic acid, then synthetic nylon-6 and nylon-66.Cyclohexanone prepared by cyclohexane in catalytic oxidation petroleum refining hydrocarbon and cyclohexanol is a kind of important industrial methodology of organic synthesis.The method of catalytic oxidation of cyclohexane has a lot, and some is also very effective.But, nearly decades, industrial cyclohexane is changed into KA oil also in a lower level, therefore finding the catalytic reaction new technology of a kind of high conversion and high selectivity, reduction pollution and energy consumption is focus and the difficult point of Chinese scholars research.
The system of catalytic oxidation of cyclohexane mainly comprises cobalt salt method catalyst system, borate method catalyst system, Gif system, bionic catalysis system, transition metal oxide and molecular sieve catalyst catalyst system and catalyzing etc.Bionic catalysis had obtained great concern in recent years, bionic catalysis system has started the research boom that catalytic oxidation of cyclohexane is prepared keto-alcohol, and metalloporphyrin is as the artificial model of oxygenase cytochrome P-450, can environment-friendly high-efficiency under temperate condition the oxidation reaction of ground catalytic hydrocarbon, be applied to the catalytic oxidation trial production of alkanes, also causing the research interest of World Science circle.But the easy polymerization of metalloporphyrin forms μ-oxygen dimer and loses its catalytic activity in homogeneous catalysis system, also can disposable consumption is complete can not reuse, make industrial production cost high and cause unnecessary waste.
At present, the effective ways that address the above problem are that the mode of imitative P450 enzyme is received metalloporphyrin on carrier, to form heterogeneous system.The stability of metalloporphyrin can be improved like this, its catalytic performance and reusability can be improved again.Chinese scholars has also been done much significant work in synthetic and protection this field of metalloporphyrin; wish by synthesising stability higher; the better novel metal porphyrin of catalytic performance; also wish to find some not only effective supported metalloporphyrins but also can improve the excellent carriers of its catalytic performance simultaneously; prepare the supported metalloporphyrin catalyst that can be applicable to wider reaction environment, to meet the needs of Industrial Catalysis development.The carrier having found has: ion exchange resin, polystyrene resin, silicone carrier, Merrifield and Argogel resin carrier; Carclazyte, aluminium oxide, molecular sieve, silica etc.Immobilized mode comprises substituting group bonding on axial coordination, porphyrin ring, room double team and adsorption etc.The present invention attempts to provide a kind of four (to carboxyl phenyl) metalloporphyrin is linked on the boiomacromolecule carrier-shitosan of porous with ionic bond and coordinate bond, the method of preparing porous type bionic catalysis material, and produce cyclohexanone and cyclohexanol by this type of catalysis material efficient catalytic air oxidation of cyclohexane.
Summary of the invention
The present invention seeks to: for overcome the conversion per pass existing in current cyclohexane oxidation technique low, selective not high, pollute the deficiency large, unit mass metalloporphyrin repeat usage is low, a kind of preparation method of porous type bionic catalysis material is provided and is applied to catalytic air oxidation cyclohexane and produce KA oil.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A porous type bionic catalysis material, is that shitosan (CTS) is dissolved in to acetic acid solution, stirs and adds ammoniacal liquor to become thickness colloid, then add four (to carboxyl phenyl) metalloporphyrin ethanolic solution, stirs, and suction filtration obtains colored colloid, by NH
4hCO
3solution adds colored colloid and stirs, and dry, then vacuum drying makes porous type bionic catalysis material, and primary raw material forms and mass fraction is:
Shitosan: 17.6 parts; 8.78 parts, glacial acetic acid; 0.0878 part of ammoniacal liquor; 0.0176 part of four (to carboxyl phenyl) metalloporphyrin; 43.9 parts, carbonic hydroammonium; 100 parts of 500 parts of distilled water and ethanol.
Above-described porous type bionic catalysis material comprises four (to carboxyl phenyl) metallic cobalt porphyrin, four (to carboxyl phenyl) manganese metal porphyrin and four (to carboxyl phenyl) metallic iron porphyrin.
The above porous type bionic catalysis material, has following following structural features formula:
Wherein: M=Mn, Co, Fe;
General metalloporphyrin structural formula as shown in the formula:
A kind of preparation method of porous type bionic catalysis material, comprise by shitosan (CTS) and be dissolved in acetic acid solution, agitation and dropping ammoniacal liquor is to pH=6.5-7 generation thickness colloid, slowly add again four (to carboxyl phenyl) metalloporphyrin ethanolic solution, stir after 24h, suction filtration obtains colored colloid, by NH
4hCO
3solution adds colored colloid and stirs, and dry, then vacuum drying makes porous type bionic catalysis material under infrared lamp, and main technological steps is:
(1) first in reaction vessel, add acetic acid solution, add pulverous shitosan, start agitator high-speed stirred 1 hour, after it dissolves completely, obtain colloid;
(2) under stirring, the colloid drops to step (1) adds ammoniacal liquor to the pH=6.5-7 of solution, stirs, and obtains thickness colloid;
(3) in reactor, add four (to carboxyl phenyl) metalloporphyrin ethanolic solution, in whipping process, shitosan and metalloporphyrin carry out acid-base reaction and complexation reaction;
(4) colored colloid step (3) being made, adds NH
4hCO
3solution, then makes it that decomposition reaction occur with infrared lamp heating and emits Bubble formation hole;
(5) vacuum drying is removed moisture content and is made porous type bionic catalysis material.
Above-described acid-base reaction and complexation reaction are at room temperature carried out, reaction time 24h.
Above-described infrared light heating is controlled at 56-65 ℃ of temperature to be carried out.
Temperature 56-65 ℃, vacuum≤0.012MPa, time 5～8h are controlled in above-described vacuum drying.
Above-described porous type bionic catalysis material is applied to catalytic air oxidation cyclohexane and produces cyclohexanone and cyclohexanol.
The above porous type bionic catalysis material application process is: cyclohexane is added in autoclave, speed of agitator is controlled at 150～250 revs/min, add again porous type bionic catalysis material, heat up, when temperature reaches 150～165 ℃, then pass into dry air, air-pressure controlling is at 0.7～1.0MPa, and air mass flow is 0.02～0.04m
3/ h, carries out oxidation reaction, and the reaction time is controlled at 3.0～4.5h.
Compare with existing cyclohexane oxidation technique, outstanding advantages of the present invention is:
This material is biological polymeric compound as catalyst used carrier shitosan, is different from inorganic carrier, and raw material sources are extensive, cheap, and belongs to renewable resource.This material can be made into porous, and specific area is larger, is beneficial to abundant generation catalytic action.Owing to thering is the effect of ion binding, particularly the coordination of the 5th longitudinal axis nitrogen-atoms, immobilized firm, and can work in coordination with four carboxylic acid group's group electron attractions in Porphyrin Molecule, promote the catalytic activity of this catalyst, greatly improved catalyst conversion per pass number; Significantly improve the conversion per pass of cyclohexane and the yield of primary product, improved catalytic efficiency.Under the effect of this type of catalyst, by cheap air oxidation of cyclohexane high yield, produce cyclohexanone and cyclohexanol, for example, use Fe porous type bionic catalysis material catalysis cyclohexane oxidation, cyclohexane conversion is 16.94%, aldehyde alcohol is selective 76.54%, catalyst turn over number 2.56 * 10
5, aldehyde alcohol productive rate 12.99%, can also reclaim and can efficiently reuse catalysis 7 times.And this type of porous type bionic catalysis material is a kind of heterogeneous catalysis, compare with common metal porphyrin homogeneous catalyst, porous type bionic catalysis material is easily separated with product, and catalysis material preparation is simple, metalloporphyrin consumption is few, cost is low, is a kind of good Industrial Catalysis material.
Accompanying drawing explanation
Fig. 1: porous type bionic catalysis material structure of the present invention;
Fig. 2: the universal architecture formula of metalloporphyrin,
Fig. 3: porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic cobalt porphyrin;
Fig. 4: porous type bionic catalysis material-tetra-(to carboxyl phenyl) manganese metal porphyrin;
Fig. 5: porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic iron porphyrin.
The specific embodiment
To the preparation method of porous type bionic catalysis material of the present invention and in the method that selective catalysis air oxidation of cyclohexane is produced cyclohexanone and cyclohexanol, be described further by the following examples.
Embodiment 1
1, the preparation of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic cobalt porphyrin
The shitosan that takes 34g is dissolved in the acetic acid solution of 600ml2%, and mechanical agitation is to becoming colloid.Under agitation dropwise drip the ammoniacal liquor of 200ml4% to the pH=7 of solution, generate thickness colloid.Four (to carboxyl phenyl) cobalt porphyrin ethanolic solution that slowly adds 100ml0.28g/L by dropping funel, stirs after 24h, and suction filtration obtains red colloid, adds 80g NH
4hCO
3, be stirred to evenly, after drying at 56 ℃ of infrared lamps, then controlling 56 ℃ of temperature, vacuum 0.007MPa, time 6h vacuum drying, makes porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic cobalt porphyrin.Its time of day figure is shown in figure
2, the application of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic cobalt porphyrin
(1) by the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) cobalt porphyrin equivalent-put in 500ml reactor, add 200ml cyclohexane, 155 ℃ of reaction temperatures, air pressure 0.8MPa, mixing speed is 200 revs/min, reaction time 4.0h, air mass flow 0.02m
3/ h.The conversion ratio of cyclohexane is 12.22%, and keto-alcohol is selective 80.69%, catalyst turn over number 1.86 * 10
5, keto-alcohol productive rate 9.86%.
1. when reaction temperature is 160 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 12.49%, and keto-alcohol is selective 79.72%, catalyst turn over number 1.91 * 10
5, keto-alcohol productive rate 9.96%.
2. when reaction temperature is 165 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 11.08%, and keto-alcohol is selective 80.03%, catalyst turn over number 1.69 * 10
5, keto-alcohol productive rate 8.86%.
(2) the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) cobalt porphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 160 ℃ of reaction temperatures, mixing speed is 250 revs/min, reaction time 4.0h, air mass flow 0.03m
3/ h.
1. when air pressure is 0.9MPa, the conversion ratio of cyclohexane is 16.29%, and keto-alcohol is selective 72.09%, catalyst turn over number 2.45 * 10
5, keto-alcohol productive rate 11.74%.
2. when air pressure is 1.0MPa, the conversion ratio of cyclohexane is 15.84%, and keto-alcohol is selective 72.83%, catalyst turn over number 2.39 * 10
5, keto-alcohol productive rate 11.53%.
(3) under the reaction temperature and 0.9MPa air pressure of 160 ℃, mixing speed is 210 revs/min, reaction time 4.0h, air mass flow 0.04m
3under/h condition.
1. the porous type bionic catalysis material of the immobilized 0.5mg of having tetra-(to carboxyl phenyl) cobalt porphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, the conversion ratio of cyclohexane is 15.32%, and keto-alcohol is selective 73.20%, catalyst turn over number 2.32 * 10
5, keto-alcohol productive rate 11.21%.
2. the porous type bionic catalysis material of the immobilized 1.5mg of having tetra-(to carboxyl phenyl) cobalt porphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, the conversion ratio of cyclohexane is 15.20%, and keto-alcohol is selective 73.40%, catalyst turn over number 2.30 * 10
5, keto-alcohol productive rate 11.16%.
Embodiment 2
The recycling of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic cobalt porphyrin
The porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) cobalt porphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 160 ℃ of reaction temperatures, air pressure 0.9MPa, mixing speed is 150 revs/min, during reaction time 3.5h, air mass flow 0.03m3/h, the conversion ratio of cyclohexane is 16.29%, and keto-alcohol is selective 72.09%, catalyst turn over number 2.45 * 10
5, keto-alcohol productive rate 11.74%.Stop after catalytic reaction at every turn, after waiting for that this catalysis material is separated with reactant mixture natural subsidence, filter, with ethanol, wash, then natural air drying, reclaims this catalysis material, then under same reaction condition for catalytic air oxidation cyclohexane, such recycling can reach 7 times, and each cyclohexane conversion is respectively: 15.89%, 16.18%, 15.75%, 15.91%, 15.64%, 15.53%, 15.23%; Keto-alcohol is selectively: 74.54%, 72.75%, 74.38%, 73.82%, 74.73%, 74.49%, 74.49%; Keto-alcohol productive rate is: 11.84%, 11.77%, 11.72%, 11.74%, 11.69%, 11.57%, 11.34%.
Embodiment 3
1, the preparation of porous type bionic catalysis material-tetra-(to carboxyl phenyl) manganese metal porphyrin
The shitosan that takes 34g is dissolved in the acetic acid solution of 600ml2%, and mechanical agitation obtains colloid.The ammoniacal liquor that dropwise drips 200ml4% under high-speed stirred, to pH=6.5, generates thickness colloid.The ethanolic solution that slowly adds 100ml0.28g/L tetra-(to carboxyl phenyl) manganoporphyrin by dropping funel, vigorous stirring 24h, suction filtration obtains glassy yellow colloid, adds 80g NH
4hCO
3, be stirred to evenly, after under infrared lamp, (60 ℃) dry, then at temperature 60 C processed, vacuum 0.010MPa, time 7h vacuum drying, makes porous type bionic catalysis material-tetra-(to carboxyl phenyl) manganese metal porphyrin.
2, the application of porous type bionic catalysis material-tetra-(to carboxyl phenyl) manganese metal porphyrin
(1) the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) manganoporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 145 ℃ of reaction temperatures, air pressure 0.8MPa, mixing speed is 180 revs/min, reaction time 4.0h, air mass flow 0.02m
3/ h.The conversion ratio of cyclohexane is 9.01%, and keto-alcohol is selective 83.46%, catalyst turn over number 1.39 * 10
5, keto-alcohol productive rate 7.52%.
1. when reaction temperature is 150 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 10.03%, and keto-alcohol is selective 81.25%, catalyst turn over number 1.54 * 10
5, keto-alcohol productive rate 8.15%.
2. when air pressure is 160 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 11.20%, and keto-alcohol is selective 79.97%, catalyst turn over number 1.71 * 10
5, keto-alcohol productive rate 8.96%.
3. when air pressure is 165 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 11.49%, and keto-alcohol is selective 78.28%, catalyst turn over number 1.76 * 10
5, keto-alcohol productive rate 8.97%.
(2) the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) manganoporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 155 ℃ of reaction temperatures, mixing speed is 200 revs/min, reaction time 3.0h, air mass flow 0.04m
3/ h.
1. when air pressure is 0.9MPa, the conversion ratio of cyclohexane is 14.67%, and keto-alcohol is selective 76.89%, catalyst turn over number 2.23 * 10
5, keto-alcohol productive rate 11.28%.
2. when air pressure is 1.0MPa, the conversion ratio of cyclohexane is 15.61%, and keto-alcohol is selective 71.98%, catalyst turn over number 2.36 * 10
5, keto-alcohol productive rate 11.23%.
(3) 155 ℃ of reaction temperatures, air pressure 0.9MPa, mixing speed is 190 revs/min, reaction time 4.0h, air mass flow 0.03m
3under/h condition.
1. the porous type bionic catalysis material of the immobilized 0.5mg of having tetra-(to carboxyl phenyl) manganoporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, the conversion ratio of cyclohexane is 14.93%, and keto-alcohol is selective 73.38%, catalyst turn over number 2.26 * 10
5, keto-alcohol productive rate 10.95%.
2. the porous type bionic catalysis material of the immobilized 1.5mg of having tetra-(to carboxyl phenyl) manganoporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, the conversion ratio of cyclohexane is 15.17%, and keto-alcohol is selective 73.32%, catalyst turn over number 1.53 * 10
5, keto-alcohol productive rate 11.12%.
Embodiment 4
The recycling of porous type bionic catalysis material-tetra-(to carboxyl phenyl) manganese metal porphyrin
The porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) manganoporphyrin equivalent is put in 500ml autoclave, added 200ml cyclohexane, 155 ℃ of reaction temperatures, air pressure 0.9MPa, mixing speed is 240 revs/min, reaction time 4.0h, air mass flow 0.03m
3/ h.The conversion ratio of cyclohexane is 14.67%, and keto-alcohol is selective 76.89%, catalyst turn over number 2.23 * 10
5, keto-alcohol productive rate 11.28%.Stop after catalytic reaction at every turn, wait for that this catalysis material is separated with reactant mixture natural subsidence, filter, with ethanol washing, then natural air drying, reclaims this catalysis material.Reusable in catalytic reaction under same reaction condition, can reach 8 times, each cyclohexane conversion is respectively: 16.71%, 15.30%, 14.50%, 15.44%, 15.01%, 15.17%, 15.41%, 14.44%; Keto-alcohol is selectively: 66.97%, 73.16%, 73.74%, 70.96%, 73.14%, 71.76%, 70.22%, 74.48%; Keto-alcohol productive rate is: 11.19%, 11.19%, 10.69%, 10.96%, 10.98%, 10.89%, 10.83%, 10.76%.
Embodiment 5
1, the preparation of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic iron porphyrin
The shitosan that takes 34g is dissolved in the acetic acid solution of 600ml2%, and mechanical agitation is to becoming colloid.Under agitation dropwise drip the ammoniacal liquor of 200ml4% to the pH=6.7 of solution, generate thickness colloid.Four (to carboxyl phenyl) ferriporphyrin ethanolic solution that slowly adds 100ml0.28g/L by dropping funel, stirs after 24h, and suction filtration obtains faint yellow colloid, adds 80g NH
4hCO
3, be stirred to evenly, after (65 ℃) dry under infrared lamp, controlling 65 ℃ of temperature, vacuum 0.012MPa, time 8h vacuum drying, makes porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic iron porphyrin.
2, the application of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic iron porphyrin
(1) the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) ferriporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 150 ℃ of reaction temperatures, air pressure 0.8MPa, mixing speed is 150 revs/min, reaction time 4.0h, air mass flow 0.03m
3/ h.The conversion ratio of cyclohexane is 16.12%, and keto-alcohol is selective 78.03%, catalyst turn over number 2.43 * 10
5, keto-alcohol productive rate 11.93%.
1. when reaction temperature is 155 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 18.67%, and keto-alcohol is selective 67.20%, catalyst turn over number 2.80 * 10
5, keto-alcohol productive rate 12.55%.
2. when air pressure is 160 ℃, other conditions are with (1), and the conversion ratio of cyclohexane is 15.73%, and keto-alcohol is selective 79.23%, catalyst turn over number 2.38 * 10
5, keto-alcohol productive rate 12.46%.
(2) the porous type bionic catalysis material of the immobilized 1.0mg of having tetra-(to carboxyl phenyl) ferriporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, 155 ℃ of reaction temperatures, mixing speed is 190 revs/min, reaction time 4.0h, air mass flow 0.04m
3/ h.
1. when air pressure is 0.9MPa, the conversion ratio of cyclohexane is 17.81%, and keto-alcohol is selective 70.38, catalyst turn over number 2.67 * 10
5, keto-alcohol productive rate 12.53%.
2. when air pressure is 0.7MPa, the conversion ratio of cyclohexane is 15.35%, and keto-alcohol is selective 75.61%, catalyst turn over number 2.32 * 10
5, keto-alcohol productive rate 11.60%.
(3) 155 ℃ of reaction temperatures, air pressure 0.8MPa, mixing speed is 200 revs/min, reaction time 4.0h, air mass flow 0.035m
3under/h condition.
1. the porous type bionic catalysis material of the immobilized 1.5mg of having tetra-(to carboxyl phenyl) ferriporphyrin equivalent is put in 500ml reactor, add 200ml cyclohexane, the conversion ratio of cyclohexane is 17.25%, and keto-alcohol is selective 75.30%, catalyst turn over number 2.60 * 10
5, keto-alcohol productive rate 12.99%.
2. the porous type bionic catalysis material of the immobilized 2mg of having tetra-(to carboxyl phenyl) ferriporphyrin equivalent is put in 500ml reactor, added 200ml cyclohexane, the conversion ratio of cyclohexane is 17.31%, and keto-alcohol is selective 72.84%, catalyst turn over number 2.60 * 10
5, keto-alcohol productive rate 12.60%.
Embodiment 6
The recycling of porous type bionic catalysis material-tetra-(to carboxyl phenyl) metallic iron porphyrin
The porous type bionic catalysis material of the immobilized 1.5mg of having tetra-(to carboxyl phenyl) ferriporphyrin equivalent is put in 500ml reactor, added 200ml cyclohexane, 155 ℃ of reaction temperatures, air pressure 0.8MPa, mixing speed is 240 revs/min, reaction time 4.0h, air mass flow 0.025m
3/ h.The conversion ratio of cyclohexane is 17.25%, and keto-alcohol is selective 75.30%, catalyst turn over number 2.60 * 10
5, keto-alcohol productive rate 12.99%.Stop after catalytic reaction at every turn, wait for that this catalysis material is separated with reactant mixture natural subsidence, filter, with ethanol washing, then natural air drying, reclaims this catalysis material.Under same reaction condition, reusable catalytic air oxidation cyclohexane 7 times, the cyclohexane conversion of each catalysis is respectively: 16.94%, 17.74%, 16.45%, 16.51%, 17.58%, 17.48%, 16.34%; Keto-alcohol is selectively: 76.54%, 72.68%, 77.91%, 76.59%, 72.09%, 71.59%, 75.97%; Keto-alcohol productive rate is: 12.97%, 12.90%, 12.81%, 12.64%, 12.68%, 12.52%, 12.42%.
Claims (4)
1. a porous type bionic catalysis material, is characterized in that: shitosan (CTS) is dissolved in to acetic acid solution, stirs and add ammoniacal liquor to become thickness colloid, then add four (to carboxyl phenyl) metalloporphyrin ethanolic solution, stir, suction filtration obtains colored colloid, by NH
4hCO
3solution adds colored colloid and stirs, and dry, then vacuum drying makes porous type bionic catalysis material, and primary raw material forms and mass fraction is:
Shitosan: 17.6 parts; 8.78 parts, glacial acetic acid; 0.0878 part of ammoniacal liquor; 0.0176 part of four (to carboxyl phenyl) metalloporphyrin; 43.9 parts, carbonic hydroammonium; 100 parts of 500 parts of distilled water and ethanol;
Described porous type bionic catalysis material comprises four (to carboxyl phenyl) metallic cobalt porphyrin, four (to carboxyl phenyl) manganese metal porphyrin and four (to carboxyl phenyl) metallic iron porphyrin, has following architectural feature:
Wherein: M=Mn, Co, Fe;
2. the preparation method of a kind of porous type bionic catalysis material according to claim 1, is characterized in that: comprise by shitosan (CTS) and be dissolved in acetic acid solution, add ammoniacal liquor extremely
ph=6.5～7, produce thickness colloid, then by dropping funel, slowly add the ethanolic solution of four (to carboxyl phenyl) metalloporphyrin, stir after 24h, and suction filtration obtains colored colloid, adds NH
4hCO
3solution, stirs, and dry, then vacuum drying makes porous type bionic catalysis material under infrared lamp, and main technological steps is:
(1) first in reaction vessel, add acetic acid solution, add pulverous shitosan (CTS), start agitator high-speed stirred 1 hour, after it dissolves completely, obtain colloid;
(2) under stirring, the colloid drops to step (1) adds ammoniacal liquor to pH=6.5～7 of solution, stirs, and obtains thickness colloid;
(3) in reactor, add four (to carboxyl phenyl) metalloporphyrin ethanolic solution, in whipping process, shitosan (CTS) and four (to carboxyl phenyl) metalloporphyrin carry out acid-base reaction and complexation reaction;
(4) product of step (3) is added to NH
4hCO
3solution, then makes it that decomposition reaction occur with infrared lamp heating and emits Bubble formation hole;
(5) vacuum drying is removed moisture content and is made porous type bionic catalysis material;
Described acid-base reaction and complexation reaction are at room temperature carried out, reaction time 24h;
Described infrared lamp heating is controlled at 56～65 ℃ of temperature to be carried out;
56～65 ℃ of temperature, vacuum≤0.012MPa, time 5～8h are controlled in described vacuum drying.
3. a kind of porous type bionic catalysis material according to claim 1, is characterized in that: be applied to catalytic air oxidation cyclohexane and produce cyclohexanone and cyclohexanol.
4. the application of a kind of porous type bionic catalysis material according to claim 1, it is characterized in that: application process is that cyclohexane is added in autoclave, speed of agitator is controlled at 150～250 revs/min, add again porous type bionic catalysis material, heat up, when temperature reaches 150～165 ℃, then pass into dry air, air-pressure controlling is at 0.7～1.0MPa, and air mass flow is 0.02～0.04m
3/ h, carries out oxidation reaction, and the reaction time is controlled at 3.0～4.5h.
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| CN103554302B (en) * | 2013-10-29 | 2015-10-21 | 广西大学 | Chitosan graft four (p-carboxyl phenyl) metalloporphyrin preparation method and application thereof |
| CN103613687B (en) * | 2013-11-27 | 2016-02-10 | 广西大学 | Chitosan four (p-sulfonic group phenyl) metalloporphyrin and preparation method and application |
| CN109046464A (en) * | 2018-08-21 | 2018-12-21 | 东北师范大学 | A kind of diatomite immobilized polyacid Quito hole bionic catalysis material and preparation method thereof |
| CN110189620B (en) * | 2019-06-21 | 2021-01-29 | 上海海洋大学 | Fish freshness visualization intelligent tag based on metalloporphyrin MOFs, and preparation method and application thereof |
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