CN110449164A - The preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst - Google Patents
The preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst Download PDFInfo
- Publication number
- CN110449164A CN110449164A CN201910886823.1A CN201910886823A CN110449164A CN 110449164 A CN110449164 A CN 110449164A CN 201910886823 A CN201910886823 A CN 201910886823A CN 110449164 A CN110449164 A CN 110449164A
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- type oxide
- oxide modified
- perofskite type
- modified activated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
Abstract
The invention discloses a kind of preparation methods of perofskite type oxide modified activated carbon supported precious metal catalyst, the noble metal is platinum or palladium, the load capacity of noble metal is 1wt%~5wt%, and preparation method includes: one, prepares perofskite type oxide modified activated carbon；Two, perofskite type oxide modified activated carbon is added in alkaline solution and is stirred evenly, heat preservation dipping obtains active carbon slurries；Three, precious metal chemical complex is dissolved in dilute hydrochloric acid, obtains active component solution；Four, active component solution is added in active carbon slurries, is stirred evenly, heat preservation dipping obtains the active carbon slurries containing noble metal；Five, reducing agent and lye are added in the active carbon slurries containing noble metal, are filtered after reduction, obtain filter cake, washed filter cake, obtain perofskite type oxide modified activated carbon supported precious metal catalyst.Noble metal catalyst reactivity prepared by the present invention is high, selectivity is high, stability is good, and metal not easily runs off in use.
Description
Technical field
The invention belongs to the preparation technical fields of noble metal catalyst, and in particular to a kind of perofskite type oxide is modified to live
The preparation method of property charcoal supported precious metal catalyst.
Background technique
Active carbon has high-specific surface area, abundant pore structure, acid and alkali resistance as precious metal catalyst agent carrier and is easy real
The advantages that existing noble metal recycling.The system of fine chemical product is widely used in using active carbon as noble metal catalyst prepared by carrier
Standby and production.Surface Physical Chemistry property possessed by different types of active carbon is different, leads to prepared catalyst performance
There are biggish differences.The research that thus precious metal catalyst is influenced about the modification of absorbent charcoal carrier, it has also become expensive
One research hotspot of metallic catalyst preparation field.Granular activated carbon is first used HCl treatment by patent CN1436591A, is reduced
Treated active carbon with oxidant is carried out oxidation processes, prevents the reduction group of activated carbon surface by the content of ashes of carrier
To the ionic palladium direct-reduction in adsorption liquid.Then it is washed, is dried, obtained one kind and be suitble to your carbon-supported gold prepared
The carrier of metal catalyst.Acid treated active carbon is using add ammonium hydroxide by the way of to carrier washing, removing Cl-, then with heating,
The mode of washing removes extra NH4+.Patent 106362719B carries out oxidation processes to graphitization active carbon using nitric acid, improves
The quantity of surface oxygen functional group, is then heat-treated under ammonia atmosphere in graphitization activated carbon capillary, make ammonia with
It is graphitized the oxygen-containing functional group reaction on activated carbon capillary surface, to remove oxygen-containing group, to make micropore size expand, from micropore
Become mesoporous, has burn tinctuer low, the features such as mesoporous rate is high, and pore-size distribution is concentrated, and stability is good.At present to absorbent charcoal carrier
Method of modifying mainly has sour processing, alkali process, oxidation processes, high-temperature heat treatment, salt treatment etc..Acid, alkali, salt treatment pass through dipping
Reach the modification to absorbent charcoal carrier impurity component and surface oxygen functional group with method for boiling, but residual in this method use process
The modifying agent stayed is difficult to remove, and a degree of pollution can be caused to environment by generating nitrogenous brine waste.Active carbon is in high temperature
After handling under atmosphere, surface hydrophobic is improved, and is unfavorable for the absorption of hydrophily reactant, is reduced catalytic performance.
Perofskite type oxide have in terms of element is assembled with crystal structure flexibly can " chemical tailoring " design it is special
Point, structure feature make many perovskite-type compounds have the physical characteristics such as light, heat, electricity, magnetic and activation binding molecule, oxidation
The chemical characteristics such as reduction, in catalysis oxidation, environmental catalysis, catalytic hydrogenation, hydrocracking, photocatalysis, solid fuel cell and change
Sensor etc. is learned to be widely studied and applied.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of preparation process letter
The preparation method of single, reproducible perofskite type oxide modified activated carbon supported precious metal catalyst.This method passes through calcium
Titanium ore type oxide modifying active carbon introduces the perofskite type oxide with special catalytic action, In in activated carbon structure
Activated carbon surface structure is modified in perofskite type oxide forming process, while active carbon is again to perofskite type oxide
Formation play structure-directing effect, the two interaction influences each other, overcomes active carbon impurity itself to the shadow of catalyst
It rings, the disadvantage that perofskite type oxide structure is single, catalytic performance is lower；By on modified active carbon, according to its structure
Feature is restored using deposition-precipitation method carried noble metal, and using formaldehyde, ensure that active metal component it is thorough restore and
The distribution of " eggshell type " and the noble metal of small size, the noble metal catalyst reactivity of preparation are generated in active carbon duct
High, selectivity height, stability are good, and metal not easily runs off in use.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of perofskite type oxide modified active
The preparation method of charcoal supported precious metal catalyst, which is characterized in that the noble metal is platinum or palladium, and the load capacity of noble metal is
The preparation method of 1wt%~5wt%, the catalyst includes:
Step 1: according to the general formula ABO of perofskite type oxide3The stoichiometric ratio of middle A and B is by soluble A salt and can
Dissolubility B salt is dissolved in deionized water, obtains mixed solution；Powdered Activated Carbon is added in the mixed solution and is stirred evenly, so
After be placed in oven and dried, finally roasted in the mixed atmosphere of nitrogen and oxygen, obtain perofskite type oxide modified active
Charcoal；The A is La, B Fe, Co, Ni or Cr；
It is stirred evenly Step 2: perofskite type oxide modified activated carbon is added in alkaline solution, in 50 DEG C~80 DEG C
Under the conditions of heat preservation dipping 1h~3h, obtain active carbon slurries；
Step 3: precious metal chemical complex is dissolved in the dilute hydrochloric acid that mass concentration is 5%~10%, it is molten to obtain active component
Liquid；The precious metal chemical complex is chloroplatinic acid or palladium chloride；
Step 4: active component solution described in step 3 is added in active carbon slurries described in step 2, stirring is equal
Even, heat preservation dipping 3h~6h, obtains the active carbon slurries containing noble metal under the conditions of 50 DEG C~80 DEG C；
Step 5: reducing agent and lye are added in the active carbon slurries described in step 4 containing noble metal, after reduction
Filtering, obtains filter cake, and filter cake is washed with deionized to no chloride ion, it is expensive to obtain the load of perofskite type oxide modified activated carbon
Metallic catalyst.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The specific surface area of Powdered Activated Carbon described in rapid one is 800m2/ g~1500m2/g。
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The salt of solubility A described in step 1 is the hydrochloride or nitrate of A, and soluble B salt is the hydrochloride or nitrate of B, the quality of A
It is the 0.5%~1.5% of Powdered Activated Carbon quality.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The temperature of stirring described in step 1 is 50 DEG C~90 DEG C, and the time of stirring is 8h~12h.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The temperature of baking oven described in step 1 is 100 DEG C~120 DEG C, and the dry time is 10h~14h.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The volumn concentration of oxygen is 10% in the mixed atmosphere of nitrogen described in step 1 and oxygen, and the temperature of the roasting is
600 DEG C~800 DEG C, the time of roasting is 5h~8h.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
Alkaline solution described in step 2 is the sodium hydrate aqueous solution that mass concentration is 2%~5% or mass concentration is 2%~5%
Potassium hydroxide aqueous solution.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
Reducing agent described in step 5 is formaldehyde, and the volume of reducing agent is 5~15 times of noble metal quality, and wherein the unit of volume is
ML, the unit of quality are g.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
Lye described in step 5 is sodium carbonate liquor or solution of potassium carbonate, and the dosage of lye is that the pH value of holding slurry system is 8.0
~9.0.
The preparation method of above-mentioned perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that
The temperature of reduction described in step 5 is 70 DEG C~90 DEG C, recovery time 2h~4h.
Compared with the prior art, the present invention has the following advantages:
1, by perofskite type oxide modified activated carbon, introducing in activated carbon structure, there is the present invention special catalysis to make
Perofskite type oxide is modified activated carbon surface structure in perofskite type oxide forming process, living simultaneously
Property charcoal structure-directing effect played to the formation of perofskite type oxide again, the two interaction influences each other, overcomes activity
Influence of charcoal impurity to catalyst itself, the disadvantage that perofskite type oxide structure is single, catalytic performance is lower.
2, the present invention is by modified active carbon, according to its design feature, using deposition-precipitation method carried noble metal,
And it is restored using formaldehyde, ensure that the thorough reduction of active metal component and generates the distribution of " eggshell type " in active carbon duct
With the noble metal of small size, the noble metal catalyst reactivity of preparation is high, selectivity is high, stability is good, is using
Metal not easily runs off in journey.
3, the present invention avoids the processing of conventional carbon acid, alkali process, oxygen by perofskite type oxide modified activated carbon
The disadvantages such as environmental pollution caused by the modification modes such as change processing, high-temperature heat treatment, salt treatment, catalyst performance be low.
4, the present invention introduces the perofskite type oxide with unique texture and special catalytic action in activated carbon structure
It is modified, the position A of perofskite type oxide can also be replaced by other ionic metal moieties with B and keep its crystal structure base
This is constant, avoids in traditional catalyst preparation process because catalyst performance caused by aided metal loss is unstable, not only
The activity of catalyst is improved, and also enhances the selectivity and stability of catalyst.
Below with reference to embodiment, technical scheme of the present invention will be described in further detail.
Specific embodiment
Embodiment 1
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is palladium, your gold
The load capacity of category be 1wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.31g La (NO3)3·6H2O and 0.29g Fe (NO3)3·9H2O is dissolved in deionized water, is obtained
To mixed solution；It is 800m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, in 50
DEG C stirring 12h, is then placed in 110 DEG C of baking oven dry 12h, finally roasts in the mixed atmosphere of nitrogen and oxygen at 600 DEG C
5h is burnt, the volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 2% that 100g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.90g step 1
Sodium hydrate aqueous solution in stir, under the conditions of 50 DEG C heat preservation dipping 2h, obtain active carbon slurries；
Step 3: the palladium chloride of the 0.10g containing palladium is dissolved in the dilute hydrochloric acid that mass concentration is 5%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 50 DEG C of conditions
Lower heat preservation impregnates 3h, obtains the active carbon slurries containing palladium；
Step 5: 1mL formaldehyde is added in the active carbon slurries in step 4 containing palladium, 70 DEG C of reductase 12 h, while using carbon
Acid sodium solution keeps slurry system pH=8.0, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
Without chloride ion in liquid, 1wt%Pd/C catalyst is obtained.
Embodiment 2
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is palladium, your gold
The load capacity of category be 2.5wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.64g LaCl3·6H2O and 0.72g Cr (NO3)3·9H2O is dissolved in deionized water, is mixed
Close solution；It is 1000m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, and stirs in 90 DEG C
8h is mixed, dry 14h is then placed in 100 DEG C of baking oven, finally roasts 7h in the mixed atmosphere of nitrogen and oxygen at 700 DEG C,
The volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 4% that 100g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.75g step 1
Potassium hydroxide aqueous solution in stir, under the conditions of 70 DEG C heat preservation dipping 2.5h, obtain active carbon slurries；
Step 3: the palladium chloride of the 0.25g containing palladium is dissolved in the dilute hydrochloric acid that mass concentration is 10%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 80 DEG C of conditions
Lower heat preservation impregnates 5h, obtains the active carbon slurries containing palladium；
Step 5: 2.5mL formaldehyde is added in the active carbon slurries in step 4 containing palladium, 80 DEG C of reduction 3h are used simultaneously
Sodium carbonate liquor keeps slurry system pH=8.5, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
It washs in liquid without chloride ion, obtains 2.5wt%Pd/C catalyst.
Embodiment 3
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is palladium, your gold
The load capacity of category be 5wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.47g La (NO3)3·6H2O and 0.31g Ni (NO3)2·6H2O is dissolved in deionized water, is obtained
To mixed solution；It is 1500m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, in 90
DEG C stirring 10h, is then placed in 120 DEG C of baking oven dry 10h, finally roasts in the mixed atmosphere of nitrogen and oxygen at 700 DEG C
8h is burnt, the volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 5% that 120g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.50g step 1
Potassium hydroxide aqueous solution in stir, under the conditions of 80 DEG C heat preservation dipping 1h, obtain active carbon slurries；
Step 3: the palladium chloride of the 0.5g containing palladium is dissolved in the dilute hydrochloric acid that mass concentration is 5%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 80 DEG C of conditions
Lower heat preservation impregnates 5h, obtains the active carbon slurries containing palladium；
Step 5: 5.0mL formaldehyde is added in the active carbon slurries in step 4 containing palladium, 90 DEG C of reduction 4h are used simultaneously
Sodium carbonate liquor keeps slurry system pH=9.0, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
It washs in liquid without chloride ion, obtains 5wt%Pd/C catalyst.
Embodiment 4
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is platinum, your gold
The load capacity of category be 1wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.62g La (NO3)3·6H2O and 0.34g NiCl2·6H2O is dissolved in deionized water, is mixed
Close solution；It is 1200m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, and stirs in 70 DEG C
10h is mixed, dry 10h is then placed in 120 DEG C of baking oven, finally roasts 6h in the mixed atmosphere of nitrogen and oxygen at 700 DEG C,
The volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 5% that 90g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.90g step 1
Sodium hydrate aqueous solution in stir, under the conditions of 70 DEG C heat preservation dipping 3h, obtain active carbon slurries；
Step 3: the chloroplatinic acid of platiniferous 0.1g is dissolved in the dilute hydrochloric acid that mass concentration is 5%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 80 DEG C of conditions
Lower heat preservation impregnates 3h, obtains the active carbon slurries of platiniferous；
Step 5: 1.0mL formaldehyde is added in the active carbon slurries of platiniferous in step 4,90 DEG C of reductase 12 h are used simultaneously
Sodium carbonate liquor keeps slurry system pH=8.0, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
It washs in liquid without chloride ion, obtains 1wt%Pt/C catalyst.
Embodiment 5
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is platinum, your gold
The load capacity of category be 3wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.93g La (NO3)3·6H2O and 0.58g FeCl3·6H2O is dissolved in deionized water, is mixed
Close solution；It is 1500m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, and stirs in 80 DEG C
10h is mixed, dry 12h is then placed in 110 DEG C of baking oven, finally roasts 5h in the mixed atmosphere of nitrogen and oxygen at 800 DEG C,
The volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 3% that 120g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.70g step 1
Sodium hydrate aqueous solution in stir, under the conditions of 65 DEG C heat preservation dipping 2h, obtain active carbon slurries；
Step 3: the chloroplatinic acid of platiniferous 0.3g is dissolved in the dilute hydrochloric acid that mass concentration is 7.5%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 50 DEG C of conditions
Lower heat preservation impregnates 4h, obtains the active carbon slurries of platiniferous；
Step 5: 1.5mL formaldehyde is added in the active carbon slurries of platiniferous in step 4,80 DEG C of reduction 3h are used simultaneously
Sodium carbonate liquor keeps slurry system pH=9.0, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
It washs in liquid without chloride ion, obtains 3wt%Pt/C catalyst.
Embodiment 6
Noble metal in the perofskite type oxide modified activated carbon supported precious metal catalyst of the present embodiment is platinum, your gold
The load capacity of category be 3wt%, catalyst the preparation method comprises the following steps:
Step 1: weighing 0.93g La (NO3)3·6H2O and 0.51g CoCl2·6H2O is dissolved in deionized water, is mixed
Close solution；It is 1300m by 20g specific surface area2The Powdered Activated Carbon of/g is added in the mixed solution and stirs evenly, and stirs in 90 DEG C
10h is mixed, dry 12h is then placed in 110 DEG C of baking oven, finally roasts 8h in the mixed atmosphere of nitrogen and oxygen at 800 DEG C,
The volumn concentration of oxygen is 10% in the mixed atmosphere, obtains perofskite type oxide modified activated carbon；
Step 2: it is 2% that 150g mass concentration, which is added, in perofskite type oxide modified activated carbon described in 9.50g step 1
Sodium hydrate aqueous solution in stir, under the conditions of 80 DEG C heat preservation dipping 3h, obtain active carbon slurries；
Step 3: the chloroplatinic acid of platiniferous 0.50g is dissolved in the dilute hydrochloric acid that mass concentration is 10%, it is molten to obtain active component
Liquid；
It is stirred evenly Step 4: active component solution is added in active carbon slurries described in step 2, in 70 DEG C of conditions
Lower heat preservation impregnates 6h, obtains the active carbon slurries of platiniferous；
Step 5: 7.5mL formaldehyde is added in the active carbon slurries of platiniferous in step 4,70 DEG C of reduction 4h are used simultaneously
Sodium carbonate liquor keeps slurry system pH=8.5, filters after reduction, obtains filter cake, and filter cake is washed with deionized to washing
It washs in liquid without chloride ion, obtains 5wt%Pt/C catalyst.
Comparative example 1
Using the method for embodiment 2, without step 1 perofskite type oxide modified activated carbon, direct commodity in use is living
Property charcoal, other steps are same as Example 2, prepare 2.5wt%Pd/C.
Comparative example 2
Using the method for embodiment 5, without step 1 perofskite type oxide modified activated carbon, direct commodity in use is living
Property charcoal, other steps are same as Example 5, prepare 3wt%Pt/C.
2,2 '-two are synthesized for being catalyzed o-chloronitrobenzene to catalyst prepared by 1-6 of the embodiment of the present invention and comparative example 1-2
Chlorine hydrazobenzene (DHB): in 1000mL stainless steel autoclave, be added 180mL toluene, 250g o-nitrochlorobenzene,
1.2g neopelex, 0.5g 2,3 dichlro 1,4 naphtho quinone, noble metal catalyst and 20% sodium hydroxide of 175g are molten
Liquid, wherein noble metal catalyst be 0.25g 3wt%Pt/C catalyst (other contents Pt/C converts by Pt content) or
0.2g2.5wt%Pd/C (other contents Pd/C converts by Pd content), sealing autoclave, in nitrogen replacement reaction kettle
Air three times, then three times with hydrogen displacement, by temperature rise to 70 DEG C, hydrogen press as 0.7MPa, start to stir, stirring rate 600r/
Min reacts 2h, stops reaction, and temperature is cooled to room temperature taking-up reaction solution, Filtration of catalyst, filtrate liquid chromatogram point
Analysis, as a result see the table below:
1 Pd/C of table is catalyzed o-chloronitrobenzene product chromatography result
| Catalyst | OCA (%) | Raw material (%) | Aniline (%) | DOB (%) | DHB (%) |
| Embodiment 1 | 2.83 | 0 | 0.11 | 0 | 96.16 |
| Embodiment 2 | 2.65 | 0 | 0.15 | 0 | 96.47 |
| Embodiment 3 | 2.78 | 0 | 0.16 | 0 | 96.13 |
| Comparative example 1 | 8.79 | 1.43 | 0.78 | 23.08 | 65.64 |
By table 1, it is apparent that Pd/C catalyst activity and selectivity with higher of the invention, with embodiment 2
It compares, without comparative example 1 prepared by perofskite type oxide modified activated carbon, there are also a small amount of residue, reactions to produce for reaction raw materials
Raw major impurity OCA and aniline are higher, and the intermediate state product DOB content of reaction is higher, and reaction product DHB yield is lower.
2 Pt/C of table is catalyzed o-chloronitrobenzene product chromatography result
| Catalyst | OCA (%) | Raw material (%) | Aniline (%) | DOB (%) | DHB (%) |
| Embodiment 4 | 2.36 | 0 | 0.08 | 0 | 96.81 |
| Embodiment 5 | 2.01 | 0 | 0.05 | 0 | 96.98 |
| Embodiment 6 | 2.43 | 0 | 0.10 | 0 | 96.79 |
| Comparative example 2 | 6.57 | 0.89 | 0.49 | 18.37 | 73.53 |
By table 2, it is apparent that Pt/C catalyst activity and selectivity with higher of the invention, with embodiment 5
It compares, without comparative example 2 prepared by perofskite type oxide modified activated carbon, reaction raw materials also have a small amount of residue, and reaction produces
Raw major impurity OCA and aniline are also higher, and the intermediate state product DOB content of reaction is higher, and reaction product DHB yield is lower.
According to the 3wt%Pt/ of above-mentioned catalytic performance test the method 2.5wt%Pd/C to embodiment 2 and embodiment 5 respectively
C catalyst carries out applying test, washs after each reaction to catalyst, applies test result and is shown in Table 3 and table 4.
3 2.5wt%Pd/C of table applies test data
4 3wt%Pt/C of table applies test data
| Apply number | DHB (%) | Reaction time (h) |
| 1 | 96.98 | 2.0 |
| 2 | 96.95 | 2.0 |
| 3 | 96.91 | 2.1 |
| 4 | 96.89 | 2.2 |
| 5 | 96.90 | 2.4 |
| 6 | 96.80 | 2.6 |
| 7 | 96.75 | 2.9 |
| 8 | 96.48 | 3.3 |
| 9 | 96.08 | 3.5 |
| 10 | 95.86 | 3.8 |
From table 3 and table 4, it is apparent that catalyst stability of the invention is good, catalyst reuse is still shown
Higher activity and product yield.
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, all according to invention skill
Art any simple modification substantially to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention
In the protection scope of scheme.
Claims (10)
1. a kind of preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst, which is characterized in that described
Noble metal is platinum or palladium, and the load capacity of noble metal is 1wt%~5wt%, and the preparation method of the catalyst includes:
Step 1: according to the general formula ABO of perofskite type oxide3The stoichiometric ratio of middle A and B is by soluble A salt and solubility B
Salt is dissolved in deionized water, obtains mixed solution；Powdered Activated Carbon is added in the mixed solution and is stirred evenly, is then placed in
It is dry in baking oven, it is finally roasted in the mixed atmosphere of nitrogen and oxygen, obtains perofskite type oxide modified activated carbon；It is described
A is La, B Fe, Co, Ni or Cr；
It is stirred evenly Step 2: perofskite type oxide modified activated carbon is added in alkaline solution, in 50 DEG C~80 DEG C conditions
Lower heat preservation impregnates 1h~3h, obtains active carbon slurries；
Step 3: precious metal chemical complex is dissolved in the dilute hydrochloric acid that mass concentration is 5%~10%, active component solution is obtained；
The precious metal chemical complex is chloroplatinic acid or palladium chloride；
Step 4: active component solution described in step 3 is added in active carbon slurries described in step 2, stir evenly, in
Heat preservation dipping 3h~6h, obtains the active carbon slurries containing noble metal under the conditions of 50 DEG C~80 DEG C；
Step 5: reducing agent and lye are added in the active carbon slurries described in step 4 containing noble metal, filtered after reduction,
Filter cake is obtained, filter cake is washed with deionized to no chloride ion, obtains perofskite type oxide modified activated carbon carried noble metal
Catalyst.
2. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the specific surface area of Powdered Activated Carbon described in rapid one is 800m2/ g~1500m2/g。
3. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the salt of solubility A described in step 1 is the hydrochloride or nitrate of A, soluble B salt is the hydrochloride or nitre of B
Hydrochlorate, the quality of A are the 0.5%~1.5% of Powdered Activated Carbon quality.
4. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the temperature of stirring described in step 1 is 50 DEG C~90 DEG C, the time of stirring is 8h~12h.
5. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the temperature of baking oven described in step 1 is 100 DEG C~120 DEG C, the dry time is 10h~14h.
6. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the volumn concentration of oxygen is 10% in the mixed atmosphere of nitrogen described in step 1 and oxygen, the roasting
The temperature of burning is 600 DEG C~800 DEG C, and the time of roasting is 5h~8h.
7. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, alkaline solution described in step 2 is the sodium hydrate aqueous solution or mass concentration that mass concentration is 2%~5%
For 2%~5% potassium hydroxide aqueous solution.
8. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, reducing agent described in step 5 is formaldehyde, the volume of reducing agent is 5~15 times of noble metal quality, wherein body
Long-pending unit is mL, and the unit of quality is g.
9. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, lye described in step 5 is sodium carbonate liquor or solution of potassium carbonate, the dosage of lye is to keep slurry system
PH value be 8.0~9.0.
10. the preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst according to claim 1,
It is characterized in that, the temperature of reduction described in step 5 is 70 DEG C~90 DEG C, recovery time 2h~4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910886823.1A CN110449164B (en) | 2019-09-19 | 2019-09-19 | Preparation method of perovskite type oxide modified activated carbon supported noble metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910886823.1A CN110449164B (en) | 2019-09-19 | 2019-09-19 | Preparation method of perovskite type oxide modified activated carbon supported noble metal catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110449164A true CN110449164A (en) | 2019-11-15 |
| CN110449164B CN110449164B (en) | 2022-03-29 |
Family
ID=68492357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910886823.1A Active CN110449164B (en) | 2019-09-19 | 2019-09-19 | Preparation method of perovskite type oxide modified activated carbon supported noble metal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110449164B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112495348A (en) * | 2020-11-11 | 2021-03-16 | 陕西浦士达环保科技有限公司 | Activated carbon capable of removing trichloromethane |
| CN116613328A (en) * | 2023-05-17 | 2023-08-18 | 东莞理工学院 | PdPt bimetallic alloy electrode material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| JP2016159224A (en) * | 2015-02-28 | 2016-09-05 | 株式会社フルヤ金属 | Supported catalyst |
| JP2016163879A (en) * | 2015-02-28 | 2016-09-08 | 株式会社フルヤ金属 | Method for producing supported catalyst |
| CN107986324A (en) * | 2017-11-17 | 2018-05-04 | 河北工业大学 | A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure |
| CN109046379A (en) * | 2018-06-29 | 2018-12-21 | 华东师范大学 | A kind of perovskite composite oxides load platinum catalyst and its preparation and application |
-
2019
- 2019-09-19 CN CN201910886823.1A patent/CN110449164B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| JP2016159224A (en) * | 2015-02-28 | 2016-09-05 | 株式会社フルヤ金属 | Supported catalyst |
| JP2016163879A (en) * | 2015-02-28 | 2016-09-08 | 株式会社フルヤ金属 | Method for producing supported catalyst |
| CN107986324A (en) * | 2017-11-17 | 2018-05-04 | 河北工业大学 | A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure |
| CN109046379A (en) * | 2018-06-29 | 2018-12-21 | 华东师范大学 | A kind of perovskite composite oxides load platinum catalyst and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 周艳波等: "活性炭表面性质对Pd/C常温氧化CO的影响", 《稀有金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112495348A (en) * | 2020-11-11 | 2021-03-16 | 陕西浦士达环保科技有限公司 | Activated carbon capable of removing trichloromethane |
| CN116613328A (en) * | 2023-05-17 | 2023-08-18 | 东莞理工学院 | PdPt bimetallic alloy electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110449164B (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101015803B (en) | Catalyst and preparing method thereof, and use in hydrogenation-dechlorination of carbon tetrachloride | |
| CN100453176C (en) | Method for reactivating deactivated palladium/carbon catalyst | |
| CN105688903B (en) | It is a kind of to be used to produce Pt/C catalyst of halogenated aniline and preparation method thereof | |
| CN102895969A (en) | Method for preparing formaldehyde room temperature oxidation catalyst | |
| CN106748813B (en) | A kind of synthesis N, the method for N '-dibenzyl-ethylenediamin | |
| CN110449164A (en) | The preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst | |
| CN105080521A (en) | Activated carbon regeneration method | |
| CN106540698A (en) | A kind of preparation method of the loading type nickel-based catalyst of chloronitrobenzene selective hydrogenation synthesis chloro aminobenzen | |
| CN109126776A (en) | A kind of preparation method and application of low reaction object diffusion steric hindrance hydrogenation catalyst | |
| CN104307477A (en) | Method for preparing nickel modified activated carbon adsorbent for lead removal of waste water | |
| CN105797719B (en) | Load type double-metal/multimetal reforming catalyst and preparation method and application for m-nitrobenzene sulfonic acid hydrogenation synthesis metanilic acid | |
| CN109174087A (en) | A kind of palladium carbon catalyst and the preparation method and application thereof | |
| TW412526B (en) | Catalyst and process for the production of vinyl acetate, and the method of preparing the catalyst | |
| CN109453779A (en) | A kind of TiO2The preparation method and application of the sepiolite supported type nickel-base catalyst of modification | |
| CN109126777A (en) | A kind of method that platinum-containing waste catalyst prepares Pt/C catalyst | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN102179245A (en) | Palladium/active carbon catalyst and application thereof in synthesizing N,N'-dibenzylethylenediamine | |
| CN113713804B (en) | Metal oxide with high specific surface area, and preparation method and application thereof | |
| CN113000052B (en) | Wet oxidation catalyst and preparation method and application thereof | |
| CN108114729A (en) | A kind of anthraquinone hydrogenation catalyst and its preparation method and application | |
| CN106064097B (en) | A kind of room temperature synthetic ammonia catalyst and preparation method thereof | |
| CN113101968A (en) | Catalyst and method for preparing glycine methyl ester and glycine by catalyzing and aminating methyl glycolate | |
| CN109806864B (en) | High-stability catalyst for preparing chlorine by oxidizing hydrogen chloride | |
| CN108144609A (en) | A kind of hydrogenolysis of glycerin prepares the preparation method of the catalyst of 1,3- propylene glycol | |
| WO2023168799A1 (en) | Carbon catalyst with highly open hierarchical pore structure as well as preparation method for and use of carbon catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |