CN109939678A - A kind of monatomic palladium catalyst and its preparation method and application - Google Patents
A kind of monatomic palladium catalyst and its preparation method and application Download PDFInfo
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- CN109939678A CN109939678A CN201910115353.9A CN201910115353A CN109939678A CN 109939678 A CN109939678 A CN 109939678A CN 201910115353 A CN201910115353 A CN 201910115353A CN 109939678 A CN109939678 A CN 109939678A
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Abstract
The invention belongs to catalyst technical fields, and in particular to a kind of monatomic palladium catalyst and its preparation method and application.The preparation method of the catalyst includes: to be impregnated into dry alumina support in the palladium salt solution of rare-earth metal nitrate modification；Then -120 to -30 DEG C at a temperature of reducing agent solution is added, it is filtering, dry sufficiently after reaction, obtain monatomic palladium catalyst.The preparation method is modified by ultralow temperature reaction condition and rare-earth metal nitrate, and the active component palladium of the monatomic catalyst of obtained palladium in high degree of dispersion and is uniformly distributed on alumina in a manner of monoatomic；Wherein, the content of palladium is 0.1-0.5wt%, and the content of rare-earth metal nitrate is 0.1-0.5wt%, and the content of aluminium oxide is 99.0-99.8wt%.Palladium metal load capacity is low in the catalyst, high catalytic efficiency, is used in anthraquinone hydrogenation and prepares in hydrogen peroxide, shows high anthraquinone hydrogenation activity and selectivity.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of monatomic palladium chtalyst prepared by low-temperature reduction
Agent is mainly used for anthraquinone hydrogenation and prepares in the technique of hydrogen peroxide.
Background technique
Hydrogen peroxide is a kind of important inorganic chemical product, as oxidant, disinfectant, bleaching agent and polymerization initiator
Deng being widely used in the fields such as weaving, papermaking, military project, medicine, food processing and environmental protection.The decomposition product of hydrogen peroxide
It is oxygen and water, it is without secondary pollution to environment, belong to green chemical.In recent years, as the application field of hydrogen peroxide is constantly opened up
Wide and from the angle of environmental protection, the demand of hydrogen peroxide is continuously increased, and hydrogen peroxide annual output in China's has surpassed thousand at present
Ten thousand tons, production capacity occupies first place in the world, and is increased every year with 10% speed.
Anthraquinone at present is the main method of large scale preparation hydrogen peroxide in the world.Technique is mainly by anthraquinone (such as 2- ethyl
Anthraquinone, 2- amyl anthraquinone) hydrogenation, hydrogen anthraquinone oxidation and hydrogen peroxide extraction etc. constitute.And anthraquinone hydrogenation is that anthraquinone production is double
The important step of oxygen water, and anthraquinone hydrogenation catalyst is one of key technology.Hydrogenation catalyst is broadly divided into palladium catalyst and orchid
Buddhist nun's Raney nickel.Palladium catalyst has become anthraquinone hydrogenation because of the activity and stability that have shown during anthraquinone hydrogenation
Most popular catalyst.However, the industrial palladium catalyst content of metal of dipping hydrogen reduction method preparation is high, active group
Divide particle size big, noble metal causes the serious wave of palladium resource using time long easy reunion in carrier surface bad dispersibility
Take.
Summary of the invention
In order to solve the above-mentioned technical problem, an object of the present invention is to provide a kind of monatomic palladium catalyst, the catalysis
Palladium metal load capacity in agent is low, disperses in carrier surface atom level, for a long time using agglomeration does not also occur, shows height
Anthraquinone hydrogenation activity and selectivity.
To achieve the goals above, technical scheme is as follows:
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.1-0.5wt%, and the content of rare-earth metal nitrate is 0.1-0.5wt%, aluminium oxide
Content is 99.0-99.8wt%.
Preferably, the rare-earth metal nitrate be one of lanthanum nitrate, cerous nitrate or yttrium nitrate or more than one
Combination.
Preferably, the alumina support is γ type alumina support, shape can be spherical, cylindrical, bar shaped or
Honeycomb or combinations thereof.
The second object of the present invention is to provide the preparation method of above-mentioned monatomic palladium catalyst, the preparation method is simple, ring
It protects, passes through the monatomic palladium chtalyst for obtaining the palladium salt solution reduction that rare-earth metal nitrate is modified under ultralow temperature reaction condition
Agent, active component palladium high degree of dispersion and are uniformly distributed on alumina in a manner of monoatomic on the alumina support.
To achieve the goals above, technical scheme is as follows:
A kind of preparation method of monatomic palladium catalyst, comprising the following steps: (1) be impregnated into dry alumina support
In the palladium salt solution of rare-earth metal nitrate modification, precursor solution is obtained；(2) -120 to -30 DEG C at a temperature of it is molten in precursor
Reducing agent solution is added in liquid, sufficiently after reaction, filtering, drying obtain monatomic palladium catalyst.
Preferably, the palladium salt solution of the rare-earth metal nitrate modification in the step (1) is prepared by the following method
Arrive: the quality according to palladium is the 0.1-0.5wt% of dry carrying alumina weight, weighs palladium salt preparation molar concentration and is
The palladium salt solution of 0.01-0.05mol/L, then by the rare earth for the 0.1-0.5wt% that quality is dry carrying alumina weight
Metal nitrate is added in palladium salt solution and modifies.
Preferably, the palladium salt in the step (1) is one of palladium chloride, palladium nitrate, chlorine palladium acid sodium or potassium chloropalladate
Or more than one combination；The solvent of palladium salt solution in the step (1) is in pure water, ethyl alcohol, ethylene glycol or glycerine
One or more kinds of combinations.
Preferably, the alumina support of the drying in the step (1) be by by alumina support at 60-120 DEG C
It is obtained after dry 6-24h in baking oven.
Preferably, the palladium salt solution that the alumina support of the drying in the step (1) is modified in rare-earth metal nitrate
Dipping 4-12 hours.
Preferably, the reducing agent in the step (2) be ascorbic acid, citric acid, hydrazine hydrate, formaldehyde, sodium borohydride and
Any one of potassium borohydride or more than one combination；The molar ratio of reducing agent and palladium in the step (2) is 5:1-
100:1；The concentration of reducing agent solution in the step (2) is 0.1-0.5mol/L；Reducing agent solution in the step (2)
Solvent be one of pure water, ethyl alcohol, ethylene glycol and glycerine or more than one combination.
Preferably, before reducing agent solution being added in precursor solution in the step (2), by the reducing agent solution with before
Liquid solution places 0.5-2h at -120 DEG C to -30 DEG C of temperature and the stirring rate of 10-600r/min in cryogenic box.
Preferably, the reducing agent solution in the step (2) be with the rate of addition of 0.1-5mL/min -120 DEG C to -
It is added drop-wise in precursor solution under 30 DEG C of temperature and the stirring rate of 10-600r/min.
Preferably, after the reducing agent solution completion of dropwise addition in the step (2), the temperature at -120 DEG C to -30 DEG C need to be continued
2-6h is reacted under the stirring rate of degree and 10-600r/min.
Preferably, the suction filtration in the step (2) be -120 to -30 DEG C at a temperature of carry out, filter used wash
Liquid is one of pure water, ethyl alcohol, ethylene glycol or glycerine or more than one combination.
Preferably, the drying in the step (2) is carried out in 60 DEG C of baking ovens.
The third object of the present invention is to provide the application of above-mentioned monatomic palladium catalyst, which is used in anthraquinone hydrogenation system
In the technique of standby hydrogen peroxide, high anthraquinone hydrogenation activity and selectivity is shown.
Beneficial effects of the present invention:
1, monatomic palladium catalyst of the invention, the particle size of palladium are 0.01-1nm, and palladium metal load capacity is low, catalysis is imitated
Rate is high, for a long time using agglomeration does not also occur.
2, the preparation method of monatomic palladium catalyst of the invention is simple and environmentally-friendly, and γ type alumina support has high ratio
Surface area and excellent pore-size distribution can make Metal Palladium dispersibility more preferable；- 120 to -30 DEG C of ultralow reaction temperature can be effective
Inhibit metal nucleation, to improve monodispersed metal atom concentration；The palladium salt solution of rare-earth metal nitrate modification, is restoring
During agent restores palladium salt, Metal Palladium can be improved in the dispersibility of carrier surface；Pass through ultralow temperature reaction condition and rare earth
The optimum choice of metal nitrate modification and each raw material and reaction condition, so that final monatomic palladium catalyst obtained
Active component palladium high degree of dispersion and is uniformly distributed on the alumina support in a manner of monoatomic on the alumina support.
3, monatomic palladium catalyst of the invention is used in anthraquinone hydrogenation and prepares in the technique of hydrogen peroxide, shows high anthraquinone
Hydrogenation activity and selectivity.Compared with industrial Pd black catalyst, anthraquinone hydrogenation performance boost 20-50%；Hydrogenation reaction is for 24 hours
Afterwards, the anthraquinone hydrogenation of industrial Pd black catalyst is selectively 90%, and monatomic palladium catalyst selectivity prepared by the present invention
It is maintained at 96% or more.
Specific embodiment:
Detailed description of the preferred embodiments below.
The present invention provides a kind of monatomic palladium catalyst, and the partial size of palladium is 0.01-1nm, and active component palladium is in height point
It dissipates and is uniformly distributed on alumina in a manner of monoatomic；Wherein, the content of palladium is 0.1-0.5wt%, rare earth metal nitric acid
Salt content is 0.1-0.5wt%, and the content of aluminium oxide is 99.0-99.8wt%.
Preferably, the rare-earth metal nitrate be one of lanthanum nitrate, cerous nitrate or yttrium nitrate or more than one
Combination.
Preferably, the alumina support is γ type alumina support, shape can be spherical, cylindrical, bar shaped or
Honeycomb or combinations thereof.
The present invention also provides the preparation methods of above-mentioned monatomic palladium catalyst, comprising the following steps: (1) by dry oxidation
Alumina supporter is impregnated into the palladium salt solution of rare-earth metal nitrate modification, obtains precursor solution；(2) in -120 to -30 DEG C of temperature
Reducing agent solution is added under degree in precursor solution, sufficiently after reaction, filtering, drying obtain monatomic palladium catalyst.
Preferably, the preparation method of the palladium salt solution of the rare-earth metal nitrate modification in the step (1), including it is as follows
Step: the quality according to palladium is the 0.1-0.5wt% of dry carrying alumina weight, weighs palladium salt preparation molar concentration and is
The palladium salt solution of 0.01-0.05mol/L, then by the rare earth for the 0.1-0.5wt% that quality is dry carrying alumina weight
Metal nitrate is added in palladium salt solution and modifies.
Preferably, the palladium salt in the step (1) is one of palladium chloride, palladium nitrate, chlorine palladium acid sodium or potassium chloropalladate
Or more than one combination；The solvent of palladium salt solution in the step (1) is in pure water, ethyl alcohol, ethylene glycol or glycerine
One or more kinds of combinations.
Preferably, the alumina support of the drying in the step (1) is by drying alumina support at 60-120 DEG C
It is obtained after dry 6-24h in case；The palladium that the alumina support of drying in the step (1) is modified in rare-earth metal nitrate
Salt solution impregnation 4-12 hours.
Preferably, the reducing agent in the step (2) be ascorbic acid, citric acid, hydrazine hydrate, formaldehyde, sodium borohydride and
Any one of potassium borohydride or more than one combination；The molar ratio of reducing agent and palladium in the step (2) is 5:1-
100:1；The concentration of reducing agent solution in the step (2) is 0.1-0.5mol/L；Reducing agent solution in the step (2)
Solvent be one of pure water, ethyl alcohol, ethylene glycol and glycerine or more than one combination.
Preferably, before reducing agent solution being added in the precursor solution in the step (2), by the reducing agent solution with before
Liquid solution places 0.5-2h at -120 DEG C to -30 DEG C of temperature and the stirring rate of 10-600r/min in cryogenic box；It is described
Reducing agent solution in step (2) is the temperature and 10-600r/ with the rate of addition of 0.1-5mL/min at -120 DEG C to -30 DEG C
It is added drop-wise in precursor solution under the stirring rate of min；After reducing agent solution completion of dropwise addition in the step (2), need to continue-
2-6h is reacted under 120 DEG C to -30 DEG C of temperature and the stirring rate of 10-600r/min.
Preferably, suction filtration in the step (2) -120 to -30 DEG C at a temperature of carry out, filter washing lotion used
For one of pure water, ethyl alcohol, ethylene glycol or glycerine or more than one combination.
Preferably, the drying in the step (2) is carried out in 60 DEG C of baking oven.
The monatomic palladium catalyst as made from above-mentioned preparation method, in the technique that anthraquinone hydrogenation prepares hydrogen peroxide,
Show high anthraquinone hydrogenation activity and selectivity.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.1wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.8wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support dry in 60 DEG C of baking ovens obtain afterwards for 24 hours；
(2) it according to the 0.1wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to ethylene glycol and glycerine volume ratio 5:5；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 5:1 according to the molar ratio of ascorbic acid and palladium, weighs ascorbic acid and prepare 10mL ascorbic acid solution；Its
In, the solvent of ascorbic acid solution is prepared according to ethylene glycol and glycerine volume ratio 5:5.
(5) by precursor solution and ascorbic acid solution at -120 DEG C of temperature and the stirring rate of 10r/min in low temperature
0.5h is placed in case；Then pass through temperature of the peristaltic pump by ascorbic acid solution with the rate of addition of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of 10r/min；After to ascorbic acid solution titration, continue at -120 DEG C
6h is reacted under temperature and the stirring rate of 10r/min.
(6) washing lotion that spent glycol and glycerine volume ratio 5:5 are prepared at -120 DEG C is filtered by vacuum；Then 60
It is dry in DEG C baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
8.2g/L, the anthraquinone hydrogenation of rear catalyst is selectively 98.8% for 24 hours.
Embodiment 2
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.5wt%, and the content of aluminium oxide is
99.0wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by by cylinder
What the γ type alumina support of shape obtained after dry 6h in 120 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium nitrate and prepares 10mL nitric acid
Then the cerous nitrate for the 0.5wt% that quality is dry carrying alumina weight is added in palladium nitrate solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium nitrate solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 12 hours in the palladium nitrate solution that cerous nitrate is modified, before obtaining
Liquid solution；
(4) it is 100:1 according to the molar ratio of citric acid and palladium, weighs citric acid and prepare 10mL citric acid solution；Wherein, lemon
The solvent of lemon acid solution is prepared according to water and ethyl alcohol volume ratio 1:9.
(5) by precursor solution and citric acid solution at -30 DEG C of temperature and the stirring rate of 600r/min in cryogenic box
Middle placement 2h；Then pass through temperature and 600r/min of the peristaltic pump by citric acid solution with the rate of addition of 5mL/min at -30 DEG C
Stirring rate under be added drop-wise in precursor solution；After to citric acid solution titration, continue the temperature and 600r/ at -30 DEG C
2h is reacted under the stirring rate of min.
(6) it is filtered by vacuum at -30 DEG C with washing lotion；Then dry in 60 DEG C of baking ovens, it obtains monatomic palladium and urges
Agent.Washing lotion is according to according to water and ethyl alcohol volume ratio 1:9 preparation.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
10.9g/L, the anthraquinone hydrogenation of rear catalyst is selectively 96.5% for 24 hours
Embodiment 3:
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.1wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.8wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by by bar shaped
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.1wt% for the carrying alumina weight that the quality of palladium is drying, weighs chlorine palladium acid sodium and prepares 10mL chlorine
Then it is molten to be added to chlorine palladium acid sodium by palladium acid sodium solution for the yttrium nitrate for the 0.1wt% that quality is dry carrying alumina weight
It is modified in liquid；Wherein, the solvent of chlorine palladium acid sodium solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the chlorine palladium acid sodium solution that yttrium nitrate is modified, before obtaining
Liquid solution；
(4) it is 5:1 according to the molar ratio of hydrazine hydrate and palladium, weighs hydrazine hydrate and prepare 10mL hydrazine hydrate solution；Wherein, it is hydrated
The solvent of hydrazine solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and hydrazine hydrate solution at -120 DEG C of temperature and the stirring rate of 100r/min in cryogenic box
Middle placement 0.5h；Then pass through temperature and 100r/ of the peristaltic pump by hydrazine hydrate solution with the speed of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of min；To hydrazine hydrate solution titration after, continue -120 DEG C temperature and
2h is reacted under the stirring rate of 100r/min.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
7.8g/L, the anthraquinone hydrogenation of rear catalyst is selectively 97.9% for 24 hours
Embodiment 4
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by by honeycomb
What the γ type alumina support of shape obtained after dry 12h in 80 DEG C of baking ovens；Prepare 30mL
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs potassium chloropalladate and prepares 10mL chlorine
Then it is molten to be added to potassium chloropalladate by palladium acid potassium solution for the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight
It is modified in liquid；Wherein, the solvent of potassium chloropalladate solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the potassium chloropalladate solution that lanthanum nitrate is modified, before obtaining
Liquid solution；
(4) it is 5:1 according to the molar ratio of formaldehyde and palladium, weighs formaldehyde and prepare 10mL formalin；Wherein, formalin
Solvent is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and formalin at -120 DEG C of temperature and the stirring rate of 100r/min in cryogenic box
Place 0.5h；Then by peristaltic pump by sodium borohydride solution with the rate of addition of 0.1mL/min -120 DEG C temperature and
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to formalin titration, continue the temperature at -120 DEG C
2h is reacted under the stirring rate of 100r/min.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
12.2g/L, the anthraquinone hydrogenation of rear catalyst is selectively 97% for 24 hours
Embodiment 5
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 100:1 according to the molar ratio of potassium borohydride and palladium, weighs potassium borohydride and prepare 10mL solution of potassium borohydride；
Wherein, the solvent of solution of potassium borohydride is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and solution of potassium borohydride at -120 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then pass through temperature of the peristaltic pump by solution of potassium borohydride with the rate of addition of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to solution of potassium borohydride titration, continue at -120 DEG C
Temperature and 100r/min stirring rate under react 2h.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
13.1g/L, the anthraquinone hydrogenation of rear catalyst is selectively 99.5% for 24 hours
Embodiment 6
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 5:1 according to the molar ratio of sodium borohydride and palladium, weighs sodium borohydride and prepare 10mL sodium borohydride solution；Its
In, the solvent of sodium borohydride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and sodium borohydride solution at -120 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then pass through temperature of the peristaltic pump by sodium borohydride solution with the rate of addition of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to sodium borohydride solution titration, continue at -120 DEG C
Temperature and 100r/min stirring rate under react 2h.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
12.6g/L, the anthraquinone hydrogenation of rear catalyst is selectively 98.2% for 24 hours.
Embodiment 7
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.5wt%, and the content of aluminium oxide is
99.0wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.5wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 5:1 according to the molar ratio of sodium borohydride and palladium, weighs sodium borohydride and prepare 10mL sodium borohydride solution；Its
In, the solvent of sodium borohydride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and sodium borohydride solution at -120 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then pass through temperature of the peristaltic pump by sodium borohydride solution with the rate of addition of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to sodium borohydride solution titration, continue at -120 DEG C
Temperature and 100r/min stirring rate under react 2h；
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
12.5g/L, the anthraquinone hydrogenation of rear catalyst is selectively 96.1% for 24 hours.
Embodiment 8
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 100:1 according to the molar ratio of sodium borohydride and palladium, weighs sodium borohydride and prepare 10mL sodium borohydride solution；
Wherein, the solvent of sodium borohydride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and sodium borohydride solution at -120 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then pass through temperature of the peristaltic pump by sodium borohydride solution with the rate of addition of 0.1mL/min at -120 DEG C
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to sodium borohydride solution titration, continue at -120 DEG C
Temperature and 100r/min stirring rate under react 2h.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
12.9g/L, the anthraquinone hydrogenation of rear catalyst is selectively 99.5% for 24 hours.
Embodiment 9
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium chloride solution and repairs by palladium solution
Decorations；Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
Spherical γ type alumina support is obtained into dry γ type alumina support after dry 12h in 80 DEG C of baking ovens；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 100:1 according to the molar ratio of sodium borohydride and palladium, weighs sodium borohydride and prepare 10mL sodium borohydride solution；
Wherein, the solvent of sodium borohydride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and sodium borohydride solution at -30 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then by peristaltic pump by sodium borohydride solution with the rate of addition of 0.1mL/min -30 DEG C temperature and
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to sodium borohydride solution titration, continue the temperature at -30 DEG C
2h is reacted under the stirring rate of degree and 100r/min.
(6) it is filtered by vacuum at -30 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
11.2g/L, the anthraquinone hydrogenation of rear catalyst is selectively 96.3% for 24 hours.
Embodiment 10
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and oxygen is evenly distributed in a manner of monoatomic
Change on aluminium；Wherein, the content of palladium is 0.5wt%, and rare-earth metal nitrate content is 0.1wt%, and the content of aluminium oxide is
99.4wt%.
Above-mentioned monatomic palladium catalyst is to be prepared by the following method:
(1) the dry γ type alumina support of 10g is weighed, wherein dry γ type alumina support is by will be spherical
γ type alumina support obtained after dry 12h in 80 DEG C of baking ovens；
(2) it according to the 0.5wt% for the carrying alumina weight that the quality of palladium is drying, weighs palladium chloride and prepares 10mL chlorination
Then the lanthanum nitrate for the 0.1wt% that quality is dry carrying alumina weight is added in palladium salt solution and modifies by palladium solution；
Wherein, the solvent of palladium chloride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(3) dry γ type alumina support is impregnated 4 hours in the palladium chloride solution that lanthanum nitrate is modified, obtains precursor
Solution；
(4) it is 100:1 according to the molar ratio of sodium borohydride and palladium, weighs sodium borohydride and prepare 10mL sodium borohydride solution；
Wherein, the solvent of sodium borohydride solution is prepared according to water and ethyl alcohol volume ratio 1:9；
(5) by precursor solution and sodium borohydride solution at -120 DEG C of temperature and the stirring rate of 100r/min in low temperature
0.5h is placed in case；Then by peristaltic pump by sodium borohydride solution with the rate of addition of 5mL/min -120 DEG C temperature and
It is added drop-wise in precursor solution under the stirring rate of 100r/min；After to sodium borohydride solution titration, continue at -120 DEG C
2h is reacted under temperature and the stirring rate of 100r/min.
(6) it is filtered by vacuum at -120 DEG C with according to the washing lotion of water and ethyl alcohol volume ratio 1:9 preparation；Then at 60 DEG C
It is dry in baking oven, obtain monatomic palladium catalyst.
The monatomic palladium catalyst that the above method is prepared, in anthraquinone hydrogenation, the hydrogenation efficiency of catalyst to be
11.9g/L, the anthraquinone hydrogenation of rear catalyst is selectively 98.6% for 24 hours.
Embodiment 11
Monatomic palladium catalyst prepared by the present invention and industrial Pd black catalyst are used into tubular glass fixed bed reaction
Device device is tested for the property comparison: the 50mL of 2- ethyl hydrazine, 1,3,5- trimethylbenzene and trioctyl phosphate composition being mixed molten
Agent and 5g catalyst are placed in fixed bed reactors, are passed through hydrogen and are started hydrogenation reaction.The result shows that being catalyzed with industrial palladium black
Agent is compared, anthraquinone hydrogenation performance boost 20-50%.Hydrogenation reaction for 24 hours after, the anthraquinone hydrogenation of industrial Pd black catalyst selects
Property is 90%, and monatomic palladium catalyst prepared by the present invention is selectively maintained at 96% or more.
The above, preferable specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and invention structure
Think of is subject to equivalent replacement or change, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of monatomic palladium catalyst, speciality are, the active component palladium of the catalyst is in high degree of dispersion and with single original
The mode of son is uniformly distributed on alumina；Wherein, the content of palladium is 0.1-0.5wt%, and the content of rare-earth metal nitrate is
0.1-0.5wt%, the content of aluminium oxide are 99.0-99.8wt%.
2. monatomic palladium catalyst according to claim 1, speciality are that the rare-earth metal nitrate is nitric acid
One of lanthanum, cerous nitrate or yttrium nitrate or more than one combination；The alumina support is γ type alumina support.
3. the preparation method of monatomic palladium catalyst according to any one of claims 1 or 2, speciality are, including
Following steps: (1) dry alumina support is impregnated into the palladium salt solution of rare-earth metal nitrate modification, it is molten obtains precursor
Liquid；(2) -120 to -30 DEG C at a temperature of reducing agent solution is added in precursor solution, it is filtering, dry sufficiently after reaction, obtain
To monatomic palladium catalyst.
4. preparation method according to claim 3, speciality are, the rare-earth metal nitrate in the step (1) is repaired
The palladium salt solution of decorations is to be prepared by the following method to obtain: the quality according to palladium is the 0.1- of dry carrying alumina weight
0.5wt% weighs palladium salt and prepares the palladium salt solution that molar concentration is 0.01-0.05mol/L, is then dry oxidation by quality
The rare-earth metal nitrate of the 0.1-0.5wt% of alumina supporter quality is added in palladium salt solution and modifies.
5. preparation method according to claim 3 or 4, speciality are, the palladium salt in the step (1) be palladium chloride,
One of palladium nitrate, chlorine palladium acid sodium or potassium chloropalladate or more than one combination；The aluminium oxide of drying in the step (1)
Modified in rare-earth metal nitrate palladium salt solution impregnation 4-12 hours of carrier.
6. preparation method according to claim 3, speciality are, the reducing agent in the step (2) be ascorbic acid,
Any one of citric acid, hydrazine hydrate, formaldehyde, sodium borohydride and potassium borohydride or more than one combination；The step (2)
In reducing agent and palladium molar ratio be 5:1-100:1；The concentration of reducing agent solution in the step (2) is 0.1-
0.5mol/L。
7. the preparation method according to claim 3 or 6, speciality are, the reducing agent solution in the step (2) be with
The rate of addition of 0.1-5mL/min is added drop-wise to precursor at -120 DEG C to -30 DEG C of temperature and the stirring rate of 10-600r/min
In solution.
8. the preparation method according to claim 3 or 6, speciality are, it is added in precursor solution in the step (2)
Temperature and 10-600r/min before reducing agent solution, by the reducing agent solution and precursor solution at -120 DEG C to -30 DEG C
0.5-2h is placed under stirring rate in cryogenic box；After reducing agent solution completion of dropwise addition in the step (2), need to continue-
2-6h is reacted under 120 DEG C to -30 DEG C of temperature and the stirring rate of 10-600r/min.
9. preparation method according to claim 3, speciality are, the suction filtration in the step (2) is -120 to -30
It is carried out at a temperature of DEG C.
10. the application of catalyst according to claim 1 or 2, speciality are, the catalyst is used in anthraquinone hydrogenation
In.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433824A (en) * | 2019-07-30 | 2019-11-12 | 北京氦舶科技有限责任公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN110639548A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398775A (en) * | 2002-08-28 | 2003-02-26 | 湖北省化学研究院 | Hydrogenation catalyst for preparing H2O2 by anthraquinone process and its prepn |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN103691437A (en) * | 2013-12-30 | 2014-04-02 | 江苏金桥盐化集团有限责任公司 | Supported palladium catalyst and preparation method thereof |
| CN105126840A (en) * | 2015-09-18 | 2015-12-09 | 武汉理工大学 | Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst |
| CN105363442A (en) * | 2014-12-12 | 2016-03-02 | 江苏金桥盐化集团有限责任公司 | Palladium catalyst for preparing hydrogen peroxide through anthraquinone hydrogenation and preparation method of palladium catalyst |
| CN109014238A (en) * | 2018-05-24 | 2018-12-18 | 清华大学 | A kind of method of low temperature liquid phase synthesized high-performance metal material |
-
2019
- 2019-02-14 CN CN201910115353.9A patent/CN109939678A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398775A (en) * | 2002-08-28 | 2003-02-26 | 湖北省化学研究院 | Hydrogenation catalyst for preparing H2O2 by anthraquinone process and its prepn |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN103691437A (en) * | 2013-12-30 | 2014-04-02 | 江苏金桥盐化集团有限责任公司 | Supported palladium catalyst and preparation method thereof |
| CN105363442A (en) * | 2014-12-12 | 2016-03-02 | 江苏金桥盐化集团有限责任公司 | Palladium catalyst for preparing hydrogen peroxide through anthraquinone hydrogenation and preparation method of palladium catalyst |
| CN105126840A (en) * | 2015-09-18 | 2015-12-09 | 武汉理工大学 | Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst |
| CN109014238A (en) * | 2018-05-24 | 2018-12-18 | 清华大学 | A kind of method of low temperature liquid phase synthesized high-performance metal material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433824A (en) * | 2019-07-30 | 2019-11-12 | 北京氦舶科技有限责任公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN110639548A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN110639548B (en) * | 2019-09-19 | 2022-06-14 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN112717926A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone hydrogenation and preparation method and application thereof |
| CN113485581A (en) * | 2021-07-02 | 2021-10-08 | 浙江鑫柔科技有限公司 | Method for forming metal grid on substrate |
| CN113731405A (en) * | 2021-09-30 | 2021-12-03 | 河南清濮智慧化工科技有限公司 | Catalyst for preparing hydrogen peroxide by anthraquinone hydrogenation and preparation method and application thereof |
| CN114177937A (en) * | 2021-12-24 | 2022-03-15 | 天津大学 | Yttrium-based supported ionic liquid bimetallic catalyst and preparation method thereof |
| CN115779899A (en) * | 2022-09-29 | 2023-03-14 | 福建省福大百阳化工科技有限公司 | Palladium-alumina catalyst and preparation method thereof |
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Application publication date: 20190628 |