CN102430405A - Loaded bimetallic nano-catalyst used for benzoic acid and sodium salt preparation as well as its preparation method - Google Patents
Loaded bimetallic nano-catalyst used for benzoic acid and sodium salt preparation as well as its preparation method Download PDFInfo
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- CN102430405A CN102430405A CN2011102725153A CN201110272515A CN102430405A CN 102430405 A CN102430405 A CN 102430405A CN 2011102725153 A CN2011102725153 A CN 2011102725153A CN 201110272515 A CN201110272515 A CN 201110272515A CN 102430405 A CN102430405 A CN 102430405A
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Abstract
Belonging to the technical field of chemical industry, the invention relates to a loaded nanometer bimetallic catalyst used for benzoic acid preparation as well as its preparation method. The catalyst of the invention takes titanium oxide as the carrier, loaded gold and silver particles as active components. The method comprises: first loading silver by an immersion method, then loading gold through a sedimentation method. The gold and silver particles have a size of 2-15 nanometers. The catalyst in the invention has small particle, good dispersibility, and strong interaction between the metals and carrier, and shows excellent activity when used for catalyzing air to oxidize benzyl alcohol directly so as to prepare benzoic acid, as well as satisfies the requirements of green chemistry. The catalyst provided in the invention is simple to separate and recover, and still has high activity after repeated application, thus boasting good industrial application prospects.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the nanocatalyst that a kind of catalytic air direct oxidation phenmethylol prepares benzoic acid and sodium benzoate.
Background technology
Benzoic acid is the simplest aromatic acid that carboxyl directly is connected with carbon atoms on a benzene ring.Benzoic acid and sodium benzoate can be used as the bacteriostatic agent of latex, toothpaste, jam or other food, and its effectiveness increases with acidity, in alkaline environment, loses antibacterial action.Benzoic acid is fat-soluble organic acid, and the molecule lipid that does not dissociate is big, sees through cells of microorganisms film kill microorganisms more easily.The antibacterial activity of its molecule that does not dissociate in acid solution is than big 100 times in neutral solution.In addition, also can dye mordant with red ink paste used for seals.Benzoic acid can be used to produce plasticizer and spices etc. as the intermediate of pharmacy and dyestuff simultaneously, also can be used as the antirust agent of steel equipment.Benzoic technology of preparation such as toluene liquid-phase air oxidation commonly used at present; Benzenyl trichlorine Hydrolyze method, phthalic anhydride liquid phase decarboxylation method, phthalic anhydride gas phase decarboxylation method; It is comparatively complicated that these prepare benzoic technology; Severe reaction conditions, temperature is higher, separates the comparatively loaded down with trivial details requirement that does not meet sustainable development and Green Chemistry of purification step.Air is a kind of desirable oxidant, and is cheap and easy to get, do not produce metal pollutant after the reaction, carries out to the direction of needs through selecting appropriate catalyst, can make to be reflected under the gentle condition.
Au catalyst is a kind of catalyst of excellence; In the oxidation of catalysis CO oxidation, steam conversion reaction and some alcohols, all shown outstanding performance; Therefore very big application potential is arranged, but do not see that so far it prepares the application aspect the benzoic acid and sodium benzoate in benzyl alcohol oxidation.In single metallic catalyst, introduce other a kind of metal formation bimetallic catalyst and can make it to have special nature.Silver catalyst also is a kind of catalyst of well behaved oxidation reaction, and preparing at ethylene epoxidizing and methanol oxidation at present has application in the formolite reaction, is that the trial of Sodium Benzoate is not succeeded so far to benzyl alcohol oxidation.The basic theory of catalysis shows that bimetallic catalyst is all influential for intensity, catalytic activity and the selectivity etc. of catalyst chemical absorption, and the interaction between component can improve the stability of catalyst.As everyone knows, Degussa P25 titanium dioxide is active carrier cheap and easy to get.Load order and the carrying method and the gold and silver ratio of passing through the modulation gold and silver of the present invention's success; Prepared the highly active bimetal nano catalyst of catalytic phenylmethanol oxidation, the technology green non-pollution that adopts simultaneously is with respect to existing benzoic acid commercial apparatus; The present invention is a kind of technology of cleaning fully; Do not relate to poisonous and harmful substance, product can directly be used for food service industry, and very high security is arranged.
The present invention uses the infusion process silver-loaded earlier; Use deposition-precipitation method load gold again; The Dor nanocatalyst of the certain load capacity for preparing can be used for this reaction of catalytic air oxidation phenmethylol, under relatively mild condition, has obtained high conversion ratio and selectivity.This process adopts the air oxidation agent of cleaning, meets requirements of green environmental protection.
Summary of the invention
The object of the present invention is to provide a kind ofly to can be used for that catalytic air direct oxidation phenmethylol prepares nanocatalyst of benzoic acid and sodium benzoate and preparation method thereof under the normal pressure condition of no solvent, with the greenization of the high activity, high yield and the building-up process that realize the benzyl alcohol oxidation reaction.
Nanocatalyst provided by the invention is to be carrier with the titanium oxide, load the bimetal nano catalyst of active component gold, silver particles.This catalyst is obtained by sedimentation load gold earlier by the infusion process silver-loaded again; Wherein, the load capacity of gold is 0.5～10% of a carrier quality, and the load capacity of silver is 0.5～10% of a carrier quality.The size of gold, silver particle is 2～15 nanometers.
The titanium dioxide carrier that the present invention uses is commercial Degussa titanium dioxide (Degussa P25), and the carrier crystal formation is that rutile and anatase mix.The gold, silver bimetal granule is dispersed in titania surface, and gold, silver particle average grain diameter 2～15 nanometers are strong with the carrier interphase interaction, and bimetal granule surface gold content is higher than body phase gold content.After the reaction, catalyst can separate with product easily.Active testing shows that this catalyst has good catalytic oxidation activity, in the reaction of catalytic air oxidation phenmethylol, has shown high catalytic activity, and benzoic separation yield can reach 92%.Catalyst has very high stability, applies mechanically repeatedly still to have greater activity, and higher economic value is arranged.
The method for preparing nano catalyst that the present invention proposes, its concrete steps are following:
According to the amount ratio of each material, in deionized water, add a certain amount of silver nitrate (AgNO respectively
3) and Degussa P25, the load capacity of control silver is 0.5～10% of a carrier quality; Stirred in water bath is to doing drying, 300 ~ 900 ℃ of roastings.
With a certain amount of above-mentioned product for preparing and an amount of gold chloride (HAuCl
4) be blended in the deionized water, adding urea and regulate pH, the load capacity of control gold is 0.5～10% of a carrier quality, stirs 1～24 h down at 60～100 ℃, suction filtration, washing, drying, 200～500 ℃ of roastings obtain the target catalyst.
Catalyst of the present invention is used for catalytic air oxidation phenmethylol under the normal pressure condition of no solvent, and its concrete steps are: under condition of no solvent, be oxidant with the air; The catalyst of above-mentioned preparation is mixed with phenmethylol; Under alkali condition (adding proper amount of sodium hydroxide), 100～300 ℃ of strong agitation were reacted 6～15 hours; Can directly prepare Sodium Benzoate, promptly get benzoic acid through hcl acidifying again.
The present invention has the following advantages:
1, the catalytic activity of catalyst is high, and selectivity is high, good stability.In the reaction of the solvent-free catalytic air oxidation phenmethylol down of normal pressure, all obtained higher activity.
2, process for synthetic catalyst is simple, can be through simple modulation load sequential system Preparation Method and modulation gold and silver load ratio, and then regulating catalyst is active.
3, carry out under this catalytic reaction normal pressure, reaction condition is gentle, uses air as oxidant, has realized the greenization and the good and economic of reaction.
4, catalyst is convenient to and the separating of product, and applies mechanically repeatedly still to have greater activity.
5, high (> 99% of product purity), need not further purification procedures, can sell.
Description of drawings
High-resolution-ration transmission electric-lens photo: Fig. 1 ~ 6 are respectively AuAg/TiO
2The catalyst of different gold and silver molar ratios.
Fig. 1. gold and silver mol ratio Au/Ag=1/3 (embodiment 1, the 1# catalyst).
Fig. 2. gold and silver mol ratio Au/Ag=1/1 (embodiment 2, the 2# catalyst).
Fig. 3. gold and silver mol ratio Au/Ag=3/1 (embodiment 3, the 3# catalyst).
Fig. 4. gold and silver mol ratio Au/Ag=1/5 (embodiment 4, the 4# catalyst).
Fig. 5. gold and silver mol ratio Au/Ag=1/7 (embodiment 5, the 5# catalyst).
Fig. 6. gold and silver mol ratio Au/Ag=1.2/1 (embodiment 6, the 6# catalyst).
The specific embodiment
The invention is further illustrated by the following examples, but enforcement of the present invention is not limited only to these embodiment.
Embodiment 1: in 50 ml, add 1.0 g titanium dioxide (Degussa P25) and mix with 6.4 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 60 ℃ of stirred in water bath are to doing 100
oDry in the C baking oven, 500 ℃ of roastings are 8 hours in the Muffle furnace, are designated as Ag/P25 (IM).In 40 ml deionized waters, add 4.2 ml 24.3mmol/L HAuCl
4Solution, 2.44 g urea and 1.0 g Ag/P25 (IM), 90 ℃ are stirred down 24 h, suction filtration, washing, drying, 300 ℃ of roastings 8 hours, the catalyst that obtains is designated as the 1# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.12 g 1# catalyst, the electromagnetic agitation reaction is 15 hours under 300 ℃ of normal pressures.
Embodiment 2: add 1.0 g titanium dioxide (Degussa P25) at the 100ml deionized water and mix with 4.3 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 100 ℃ of stirred in water bath are to doing 120
oDry in the C baking oven, 800 ℃ of roastings are 24 hours in Muffle furnace, are designated as Ag/P25 (IM).In 20 ml deionized waters, add 8.4 ml 24.3mmol/L HAuCl
4Solution and 1.0g Ag/P25 (IM), be stirred to dried, 60
oDry in the C baking oven, 500 ℃ of roastings 12 hours, the catalyst that obtains is designated as the 2# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.4 g NaOH, 0.12 g 2# catalyst, the electromagnetic agitation reaction is 10 hours under 250 ℃ of normal pressures.
Embodiment 3: in 10 ml deionized waters, add 2.1 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 0.76 g urea and 1.0 g P25, be stirred under 80 ℃ dried, suction filtration, washing, drying, 300 ℃ of roastings 2 hours are designated as Ag/P25 (DP).In 80 ml deionized waters, add 12.5 ml 24.3mmol/L HAuCl
4Solution and 1.0 g Ag/P25 (DP), be stirred to dried, 100
oDry in the C baking oven, 200 ℃ of roastings 2 hours, the catalyst that obtains is designated as the 3# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.05 g 3# catalyst, the electromagnetic agitation reaction is 6 hours under 100 ℃ of normal pressures.
Embodiment 4: in the 40ml deionized water, add 18.6mL 47.6 mmol/L liquor argenti nitratis ophthalmicuses, and 2.5 g urea and 1.0 g P25,70 ℃ are stirred 1 h down, suction filtration, washing, drying, 700 ℃ of roastings 12 hours are designated as Ag/P25 (DP).In 45 ml deionized waters, add 7.3ml 24.3 mmol/L HAuCl
4Solution, 2.13 g urea and 1.0g Ag/P25 (DP), 75 ℃ are stirred down 5h, suction filtration, washing, drying, 300 ℃ of roastings 4 hours, the catalyst that obtains is designated as the 4# catalyst.Use the reaction condition of this catalyst: the 1.08g phenmethylol, 0.45g NaOH, 0.08g 4# catalyst, the electromagnetic agitation reaction is 8 hours under 180 ℃ of normal pressures.
Embodiment 5: in 30 ml deionized waters, add 2.1 ml, 24.3 mmol/L HAuCl
4Solution, 2.11 g urea and 1.0 g P25,70 ℃ are stirred down 3h, suction filtration, washing, drying, 200 ℃ of roastings 6 hours are designated as Au/P25 (DP).In 50 ml deionized waters, add 7.5 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 2.5 g urea and 1.0 g Au/P25 (DP), 90 ℃ are stirred 3h down, suction filtration, washing, drying, 600 ℃ of roastings 4 hours, the catalyst that obtains is designated as the 5# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 5# catalyst, the electromagnetic agitation reaction is 6 hours under 300 ℃ of normal pressures.
Embodiment 6: in 35 ml deionized waters, add 10ml 24.3mmol/L HAuCl
4Solution, 3.0g urea and 1.0g P25,90 ℃ are stirred down 5h, suction filtration, washing, drying, 300 ℃ of roastings 5 hours are designated as Au/P25 (DP).Add 1.0 g Au/P25 (DP) at 30 ml deionized waters and mix, extremely do 60 in 60 ℃ of stirred in water bath with 4.3 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses
oDry in the C baking oven, 550 ℃ of roastings are 4 hours in Muffle furnace, and the catalyst that obtains is designated as the 6# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.45 g NaOH, 0.09g 6# catalyst, the electromagnetic agitation reaction is 7 hours under 250 ℃ of normal pressures.
Embodiment 7: in 40 ml deionized waters, add 8.4 ml 24.3mmol/L HAuCl
4Solution and 1.0 g P25, be stirred to dried, 100
oDry in the C baking oven, 450 ℃ of roastings 4 hours are designated as Au/P25 (IM).Add 1.0 g Au/P25 (IM) at 50 ml deionized waters and mix, extremely do 100 in 60 ℃ of stirred in water bath with 4.3 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses
oDry in the C baking oven, 550 ℃ of roastings are 4 hours in Muffle furnace, and the catalyst that obtains is designated as the 7# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5g NaOH, 0.1 g 7# catalyst, the electromagnetic agitation reaction is 8 hours under 150 ℃ of normal pressures.
Embodiment 8: in 40 ml deionized waters, add 9.4 ml, 24.3 mmol/L HAuCl
4Solution and 1.0 g P25, be stirred to dried, 100
oDry in the C baking oven, 500 ℃ of roastings 24 hours are designated as Au/P25 (IM).In 50 ml deionized waters, add 4.5 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 2.3 g urea and 1.0 g Au/P25 (IM), 80 ℃ are stirred 6h down, suction filtration, washing, drying, 900 ℃ of roastings 24 hours, the catalyst that obtains is designated as the 8# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.4 g NaOH, 0.15 g 8# catalyst, the electromagnetic agitation reaction is 15 hours under 200 ℃ of normal pressures.
Embodiment 9: in 50 ml deionized waters, add 3.2 ml, 24.3 mmol/L HAuCl
4Solution, 21.4 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses and 1.0 g P25, be stirred to dried, 100
oDry in the C baking oven, 500 ℃ of roastings 4 hours, the catalyst that obtains is designated as the 9# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.15 g 9# catalyst, the electromagnetic agitation reaction is 14 hours under 250 ℃ of normal pressures.
Embodiment 10: in 20 ml deionized waters, add 23.4 ml 24.3mmol/L HAuCl
4Solution, 1.0mL 47.6 mmol/L liquor argenti nitratis ophthalmicuses, 5.3g urea and 1.0 g P25,90 ℃ are stirred down 1 h, suction filtration, washing, drying, 500 ℃ of roastings 8 hours, the catalyst that obtains is designated as the 10# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5g NaOH, 0.1 g 10# catalyst, the electromagnetic agitation reaction is 12 hours under 280 ℃ of normal pressures.
Embodiment 11: in 48 ml deionized waters, add 2 ml 24.3mmol/L HAuCl
4Solution, 2.92 g urea and 0.6 g P25,90 ℃ are stirred down 4h, suction filtration, washing, drying, 300 ℃ of roastings 3 hours, the catalyst that obtains is designated as the 11# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 11# catalyst, the electromagnetic agitation reaction is 10 hours under 200 ℃ of normal pressures.
Embodiment 12: add 1.0 g titanium dioxide (Degussa P25) at 22 ml deionized waters and mix with 21.4mL 47.6 mmol/L liquor argenti nitratis ophthalmicuses, extremely do 100 in 80 ℃ of stirred in water bath
oDry in the C baking oven, 500 ℃ of roastings are 5 hours in Muffle furnace, are designated as Ag/P25 (IM).In 63 ml deionized waters, add 1.1 ml 24.3mmol/L HAuCl
4Solution, 3.64 g urea and 1.0 g Ag/P25 (IM), 90 ℃ are stirred down 3 h, suction filtration, washing, drying, 300 ℃ of roastings 5 hours, the catalyst that obtains is designated as the 12# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.15 g 12# catalyst, the electromagnetic agitation reaction is 12 hours under 280 ℃ of normal pressures.
Embodiment 13:1.08 g phenmethylol, 0.5 g NaOH, 0.1 g 1# catalyst, the electromagnetic agitation reaction is 9 hours under 200 ℃ of normal pressures.
Embodiment 14: add 1.0 g titanium dioxide (Degussa P25) at 64 ml deionized waters and mix with 6.4 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, extremely do 100 in 60 ℃ of stirred in water bath
oDry in the C baking oven, 500 ℃ of roastings are 4 hours in Muffle furnace, are designated as Ag/P25 (IM).In 21 ml deionized waters, add 4.2 ml 24.3mmol/L HAuCl4 solution, 1.22 g urea and 1.0 g Ag/P25 (IM), 90 ℃ are stirred 1 h down, suction filtration, washing, drying, 300 ℃ of roastings 4 hours, the catalyst that obtains is designated as the 13# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 13# catalyst, the electromagnetic agitation reaction is 10 hours under 200 ℃ of normal pressures.
Embodiment 15: add 1.0 g titanium dioxide (Degussa P25) at 85 ml deionized waters and mix with 8.5 mL, 47.6 mmol/L liquor argenti nitratis ophthalmicuses, extremely do 90 in 70 ℃ of stirred in water bath
oDry in the C baking oven, 500 ℃ of roastings are 5 hours in Muffle furnace, and the catalyst that obtains is designated as the 14# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.15 g 14# catalyst, the electromagnetic agitation reaction is 13 hours under 200 ℃ of normal pressures.
Embodiment 16:1.08 g phenmethylol, 0.3 g NaOH, 0.15 g 1# catalyst, the electromagnetic agitation reaction is 10 hours under 150 ℃ of normal pressures.
Embodiment 17:1.08 g phenmethylol, 0.5 g NaOH, 0.2 g 1# catalyst, the electromagnetic agitation reaction is 12 hours under 150 ℃ of normal pressures.
Embodiment 18:1.08 g phenmethylol, 0.5 g NaOH, 0.08 g 1# catalyst, the electromagnetic agitation reaction is 8 hours under 130 ℃ of normal pressures.
Embodiment 19:1.08 g phenmethylol, 0.5 g NaOH, 0.1 g 1# catalyst, the electromagnetic agitation reaction is 8 hours under 200 ℃ of normal pressures.
Embodiment 20:1.08 g phenmethylol, 0.5 g NaOH, 0.1 g 1# catalyst, the electromagnetic agitation reaction is 8 hours under 250 ℃ of normal pressures.
Embodiment 21: after finished reaction 14 (embodiment 14), catalyst was centrifugal, washing, 110 ℃ dry 12 hours down, the catalyst that obtains is designated as the 15# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 15# catalyst, the electromagnetic agitation reaction is 10 hours under 200 ℃ of normal pressures.
Embodiment 22: after finished reaction 21 (embodiment 21), catalyst was centrifugal, washing, 80 ℃ dry 12 hours down, the catalyst that obtains is designated as the 16# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 16# catalyst, the electromagnetic agitation reaction is 10 hours under 200 ℃ of normal pressures.
Embodiment 23: after finished reaction 22 (embodiment 22), catalyst was centrifugal, washing, 120 ℃ dry 12 hours down, the catalyst that obtains is designated as the 17# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 17# catalyst, the electromagnetic agitation reaction is 10 hours under 200 ℃ of normal pressures.
Embodiment 24: after finished reaction 23 (embodiment 23), catalyst was centrifugal, washing, 100 ℃ dry 12 hours down, the catalyst that obtains is designated as the 18# catalyst.Reaction condition: 1.08 g phenmethylols, 0.5 g NaOH, 0.1 g 18# catalyst, the electromagnetic agitation reaction is 13 hours under 250 ℃ of normal pressures.
Embodiment 25: after finished reaction 24 (embodiment 24), catalyst was centrifugal, washing, 120 ℃ dry 12 hours down, the catalyst that obtains is designated as the 19# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.4 g NaOH, 0.1 g 19# catalyst, the electromagnetic agitation reaction is 14 hours under 250 ℃ of normal pressures.
Embodiment 26: after finished reaction 25 (embodiment 25), catalyst was centrifugal, washing, 90 ℃ dry 12 hours down, the catalyst that obtains is designated as the 20# catalyst.Use the reaction condition of this catalyst: 1.08 g phenmethylols, 0.5 g NaOH, 0.15 g 220# catalyst, the electromagnetic agitation reaction is 15 hours under 250 ℃ of normal pressures.
Table 1. series A uAg/TiO
2The active result of reaction condition and benzoic acid synthetic reaction
| Embodiment | Catalyst | Reaction temperature (℃) | Reaction time (h) | Benzoic acid mole yield (%) |
| 1 | 1＃ | 300 | 15 | 90.4 |
| 2 | 2＃ | 250 | 10 | 87.6 |
| 3 | 3＃ | 100 | 6 | 70.1 |
| 4 | 4＃ | 180 | 8 | 81.4 |
| 5 | 5＃ | 300 | 6 | 62.8 |
| 6 | 6＃ | 250 | 7 | 73.9 |
| 7 | 7＃ | 150 | 8 | 75.0 |
| 8 | 8＃ | 200 | 15 | 78.6 |
| 9 | ? 9＃ | 250 | 14 | 81.0 |
| 10 | 10＃ | 200 | 10 | 85.6 |
| 11 | 11＃ | 200 | 10 | 67.4 |
| 12 | 12＃ | 280 | 12 | 87.2 |
| 13 | 1# | 200 | 9 | 85.6 |
| 14 | 13# | 200 | 10 | 87.3 |
| 15 | 14＃ | 200 | 13 | 70.1 |
| 16 | 1# | 150 | 10 | 73.2 |
| 17 | 1# | 150 | 12 | 75.1 |
| 18 | 1# | 130 | 8 | 70.3 |
| 19 | 1# | 200 | 8 | 75.7 |
| 20 | 1# | 250 | 8 | 76.0 |
| 21 | 15# | 200 | 10 | 92.1 |
| 22 | 16# | 200 | 10 | 90.6 |
| 23 | 17# | 200 | 10 | 88.3 |
| 24 | 18# | 250 | 13 | 86.7 |
| 25 | 19# | 250 | 14 | 85.1 |
| 26 | 20# | 250 | 15 | 81.6 |
Claims (3)
1. one kind is used for the catalytic air oxidation phenmethylol and prepares benzoic loaded nano bimetallic catalyst, it is characterized in that with titanium dioxide being carrier, and load gold, silver particle, is obtained by sedimentation load gold earlier by the infusion process silver-loaded as active component again; Wherein, the load capacity of gold is 0.5～10% of a carrier quality, and the load capacity of silver is 0.5～10% of a carrier quality; The size of gold, silver particle is 2～15 nanometers.
2. the preparation method of loaded nano bimetallic catalyst as claimed in claim 1 is characterized in that concrete preparation process is following:
According to the amount ratio of each material, in deionized water, add a certain amount of silver nitrate and Degussa titanium dioxide respectively, the load capacity of control silver is 0.5～10% of a carrier quality; Stirred in water bath is to doing drying, 300 ~ 900 ℃ of roastings;
The product and an amount of gold chloride of above-mentioned preparation are blended in the deionized water, add urea and regulate pH, the load capacity of control gold is 0.5～10% of a carrier quality; Stir 1～24 h, suction filtration, washing down at 60～100 ℃; Drying, 200～500 ℃ of roastings obtain the target catalyst.
3. loaded nano bimetallic catalyst as claimed in claim 1 prepares the application in the benzoic acid and sodium benzoate at the catalytic air oxidation phenmethylol, it is characterized in that concrete reaction condition is following: under condition of no solvent, be oxidant with the air; Said catalyst is mixed with phenmethylol; Under alkali condition, 100～300 ℃ of stirrings were reacted 6～15 hours; Be prepared into Sodium Benzoate, promptly get benzoic acid through hcl acidifying again.
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| CN103007932A (en) * | 2012-12-11 | 2013-04-03 | 山东大学 | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst |
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| CN103007932B (en) * | 2012-12-11 | 2014-09-03 | 山东大学 | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst |
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