CN106582620B - A kind of preparation method of high-dispersion loading type noble metal powder catalyst - Google Patents
A kind of preparation method of high-dispersion loading type noble metal powder catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of high-dispersion loading type noble metal powder catalyst, this method are as follows: one, by powder carrier be uniformly mixed to form suspension with deionized water；Noble metal precursor body is dissolved in deionized water, aqueous phase solution is formed；Two, suspension is added in stirring autoclave slurry reactor and is stirred, adjust the pH value of suspension as alkalinity；Three, aqueous phase solution is added to after being atomized in stirring autoclave slurry reactor, then precious metal ion is precipitated in the form of precious metal precipitation object, and adsorbs the surface for the powder carrier being deposited in suspension, forms uniform slurry；Four, aging is stirred to slurry at a certain temperature, precious metal precipitation object is anchored on powder carrier surface, then restores precious metal precipitation object, filtering and washing, obtains high-dispersion loading type noble metal powder catalyst.Preparation process of the present invention is simple, easily controllable, is suitable for industrialized production high-dispersion loading type noble metal powder catalyst.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of high-dispersion loading type noble metal powder catalyst
Preparation method.
Background technique
High-dispersion loading type noble metal powder catalyst has catalytic activity is high, selectivity is good, service life cycle is long etc.
Feature is used extensively in fields such as petrochemical industry, pharmacy, fine chemistry industry and organic syntheses, is had a very important role.From
German E. Jacob in 1875 receives the conspicuous contact subtraction unit for establishing First production oleum in Creutz, and manufactures
Required platinum catalyst, this is the pioneer of solid industrial catalyst.Noble metal platinum is first industrial catalyst, present noble metal
It has been the catalytic active component in many essential industry catalyst, high-dispersion loading type noble metal powder catalyst is a kind of wide
The environmental friendly catalysis material of general application, the reactions such as PARA FORMALDEHYDE PRILLS(91,95) low-temperature catalytic burning have good catalytic effect, and in ammino
Have at reaction, organic pollutant elimination plus hydrogen and Reforming catalyst reaction, gas sensor, fuel cell etc. potential or real
Border application value.
Currently, there are many production methods, such as heavy in the preparation and production process of high-dispersion load noble metal powder catalyst
It is precipitated area method, infusion process, roll coating process, the precipitation method, mixing method, ion-exchange, gas phase synthesis method etc..
Patent CN104399455 discloses a kind of preparation method of palladium carbon catalyst, and palladium chloride solution is sprayed to fluidisation
Handling on the active carbon with oxidation processes in bed by soda acid, is passed through hydrogen reducing, finally uses pure water.But the preparation side
Powdered active carbon is kept fluidized state by air-introduced machine by method in a fluidized bed, on the one hand inevitably results in powder activity
Charcoal more seriously causes active carbon to move at random in a fluidized bed as flow of warm nitrogen gas sprays fluidized bed, with palladium chloride
The contact probability of solution is unequal, the uneven distribution so as to cause active component palladium in activated carbon surface, and powder activity
After the adsorbing chlorinated palladium solution of charcoal, it is easy to which tacky viscous wall has been further exacerbated by palladium chloride in the uneven dispersion of active carbon, catalysis
Activity is difficult to be not fully exerted.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, providing, a kind of high dispersive is negative
The preparation method of load type noble metal powder catalyst.The preparation method can obtain the narrow active metal component of particle size distribution range
It is highly homogeneously dispersed in dust carrier surface, effectively improves the preparation efficiency and effect of carried noble metal fine catalyst
Fruit, the Active components distribution for solving the carried noble metal fine catalyst of production method preparation in the prior art are uneven
It is even, easy to reunite, the industrialization technical problems such as difficulty is big.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of high-dispersion loading type noble metal powder
The preparation method of catalyst, which is characterized in that method includes the following steps:
Step 1: water-insoluble powder carrier is uniformly mixed to form suspension with deionized water；Before noble metal
It drives body to be dissolved in deionized water, forms aqueous phase solution；In the suspension mass percentage of powder carrier be 1%~
50%, the mass concentration of noble metal precursor body is 0.01g/mL~0.20g/mL in the aqueous phase solution；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, start to stir, and adjusts outstanding
The pH value of turbid is alkalinity；
Step 3: aqueous phase solution described in step 1 to be added to the stirring equipped with alkaline suspension in step 2 after being atomized
In autoclave slurry reactor, the precious metal ion of the aqueous phase solution is analysed in the form of precious metal precipitation object under alkaline condition
Out, it is rapidly dispersed into suspension under agitation, and adsorbs the surface for the powder carrier being deposited in the suspension,
Eventually form uniform slurry；
Step 4: temperature be 0 DEG C~100 DEG C, stirring under conditions of to slurry described in step 3 carry out aging 1h~
48h, the precious metal precipitation object are anchored on powder carrier surface, then pass through wet chemistry reduction method for precious metal precipitation object
It is reduced into noble metal, filtering and washing, obtains high-dispersion loading type noble metal powder catalyst.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, which is characterized in that institute in step 1
Stating carrier is aluminium oxide, calcium carbonate, active carbon, barium sulfate, titanium dioxide, silica, molecular sieve or ceramics.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, which is characterized in that described in step 1
Noble metal precursor body is the water solubilityization of the water soluble compound of Pt, the water soluble compound of Pd, the water soluble compound of Ru, Rh
Close one or more of object, the water soluble compound of Ir, the water soluble compound of Au and water soluble compound of Ag.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, which is characterized in that institute in step 1
The mass content for stating noble metal in noble metal precursor body is the 0.01%~30% of the powder carrier quality.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, which is characterized in that institute in step 1
The mass content for stating noble metal in noble metal precursor body is the 1%~10% of the powder carrier quality.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, which is characterized in that lead in step 2
Cross at least one of urea, ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and saleratus object
Matter adjusts the pH value of suspension to alkalinity.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, which is characterized in that adjusted in step 2
The pH value of suspension is saved to 8~10.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, which is characterized in that institute in step 3
Aqueous phase solution is stated to be sprayed by high-pressure fog mouth, high-pressure atomizer or ultrasonic atomizer into atomizing particle, the atomizing particle
Partial size is 0.5um~5um.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, which is characterized in that institute in step 4
Stating reducing agent used in wet chemistry restoring method is citric acid, oxalic acid, formaldehyde, formic acid, hydrazine hydrate, sodium borohydride, hydroboration
One or more of potassium, hydrazine hydrochloride, ascorbic acid and polyalcohol, the additive amount of the reducing agent are described in step 1
2~10 times of noble metal mass content in noble metal precursor body.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, which is characterized in that lead in step 4
Plate and frame filter press, centrifuge or negative pressure funnel is crossed to be filtered.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, which is characterized in that lead in step 4
Plate and frame filter press, centrifuge and negative pressure funnel is crossed to be filtered.
Compared with the prior art, the present invention has the following advantages:
1, executing in preparation method provided by the invention in precipitating deposition step uses spray atomization by noble metal active group
Divide presoma aqueous phase solution to be added to stirring autoclave slurry reactor with atomizing type, realizes precious metal ion and be dispersed in
Carrier suspension surface, while spray atomization, catalyst carrier is turned under strong stirring in stirring autoclave slurry reactor
Rolling, therefore contact effect of the catalyst carrier improved with active material, therefore while promoting catalyst preparation efficiency, it protects
The precipitating deposition effect of catalyst carrier is demonstrate,proved.In addition, the adding manner of spray atomization effectively control precious metal ion with it is suspended
The combination of basic group in liquid realizes the size Control of precious metal precipitation, can under equal conditions use less work
Property component solution realize catalyst carrier equably high degree of dispersion precipitate deposition step.
2, noble metal is atomized to dust carrier surface, dramatically by the present invention in stirring autoclave slurry reactor
It is equably highly dispersed on dust carrier surface, gives full play to effect of the noble metal as active component, improve product
Performance and consistency, and preparation method of the invention, simple process, process operation is easily controllable, has high practicability,
Be conducive to industrialized production.
3, the preparation method of high-dispersion loading type noble metal powder catalyst of the invention, simple process, easily operated control
System, is able to produce high-dispersion loading type noble metal powder catalyst, noble metal active component is highly dispersed at carrier surface, has
High catalytic activity and selectivity.
Technical solution of the present invention is described in further detail below by drawings and examples.
Detailed description of the invention
Fig. 1 is the 5%Pd/C catalysis in high-dispersion loading type noble metal powder catalyst prepared by the embodiment of the present invention 11
The SEM photograph of agent.
Fig. 2 is the 5%Pd/C catalysis in high-dispersion loading type noble metal powder catalyst prepared by the embodiment of the present invention 17
The TEM photo of agent.
Specific embodiment
Embodiment 1
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered alumina carrier and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powdered alumina carrier is 30% in the suspension, noble metal in the aqueous phase solution
The mass concentration of presoma is 0.05g/mL；The mass content of palladium is the powdered alumina carrier quality in the palladium chloride
1%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium carbonate adjusts suspension is 9.2；
Step 3: being the atomization of 3um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure atomizer
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on alumina support, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 50 DEG C, stirring rate is 1000r/min
For 24 hours, the palladium dydroxide is anchored on the surface of powdered alumina carrier, then uses sodium borohydride reduction palladium dydroxide, also
It is former product is added to negative pressure funnel to be after the reaction was completed filtered and washed to no chloride ion, it is then dry at 100 DEG C, it obtains
High dispersive 1%Pd/Al2O3Fine catalyst；The additive amount of the sodium borohydride is palladium content in palladium chloride described in step 1
2.5 again.
Embodiment 2
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered titania support and deionized water are uniformly mixed to form suspension；Potassium chloroplatinate dissolution
In deionized water, aqueous phase solution is formed；
The mass percentage of powdered titania support is 40% in the suspension, chlorine platinum in the aqueous phase solution
The mass concentration of sour potassium is 0.03g/mL；The mass content of platinum is the powdered TiO 2 carrying constitution in the potassium chloroplatinate
The 5% of amount；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium carbonate adjusts suspension is 8.5；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and platinum ion is under alkaline condition with platinic hydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on titania support, formed uniform
Slurry；
Step 4: by slurry aging described in step 3 under conditions of temperature is 85 DEG C, stirring rate is 1000r/min
18h, the platinic hydroxide are anchored on the surface of powdered titania support, then use potassium borohydride reduction palladium dydroxide,
Product is added to centrifuge after the completion of reduction reaction to be filtered and washed to no chloride ion, the then drying at 100 DEG C obtains
To high dispersive 5%Pt/TiO2Fine catalyst；The additive amount of the sodium borohydride is that palladium contains in potassium chloroplatinate described in step 1
4 times of amount.
Embodiment 3
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Rhodium chloride is dissolved in
In deionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 15% in the suspension, tri-chlorination in the aqueous phase solution
The mass concentration of rhodium is 0.15g/mL；The mass content of rhodium is the powdered active carbon carrier quality in the rhodium chloride
10%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium carbonate adjusts suspension is 9.8；
Step 3: being the atomization of 3um with partial size after aqueous phase solution described in step 1 is atomized by ultrasonic atomizer
Grain sprays into stirring autoclave slurry reactor, and rhodium ion is under alkaline condition with rhodium hydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: under conditions of temperature is 100 DEG C, stirring rate is 1000r/min that slurry described in step 3 is old
Change for 24 hours, the rhodium hydroxide is anchored on the surface of powder activated high-area carbon, then restores palladium dydroxide, reduction using formaldehyde
Product is added to centrifuge after the reaction was completed to be filtered and washed to no chloride ion, high dispersive 10%Rh/C powder is obtained and urges
Agent, moisture content 58%；The additive amount of the formaldehyde is 10 times of rhodium content in rhodium chloride described in step 1.
Embodiment 4
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Iridous chloride is dissolved in
In deionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 1% in the suspension, tri-chlorination in the aqueous phase solution
The mass concentration of iridium is 0.20g/mL；The mass content of iridium is the powdered active carbon carrier quality in the iridous chloride
3%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium carbonate adjusts suspension is 8.8；
Step 3: being the atomization of 3um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and iridium ion is under alkaline condition with hydroxide iridium precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: under conditions of temperature is 100 DEG C, stirring rate is 1000r/min that slurry described in step 3 is old
Change 48h, the hydroxide iridium is anchored on the surface of powder activated high-area carbon, potassium borohydride reduction hydroxide iridium is then used,
Product is added to centrifuge after the completion of reduction reaction to be filtered and washed to no chloride ion, obtains high dispersive 3%Ir/C powder
Last catalyst, moisture content 65%；The additive amount of the sodium borohydride is 10 times of iridium content in iridous chloride described in step 1.
Embodiment 5
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered silica carrier and deionized water are uniformly mixed to form suspension；Ruthenium trichloride dissolution
In deionized water, aqueous phase solution is formed；
The mass percentage of powdered silica carrier is 5% in the suspension, trichlorine in the aqueous phase solution
The mass concentration for changing ruthenium is 0.12g/mL；The mass content of ruthenium is the powdered silica carrier matter in the ruthenium trichloride
The 5% of amount；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium carbonate and sodium carbonate adjust suspension is 7.8；
Step 3: being the atomization of 3um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and ruthenium ion is under alkaline condition with hydroxide ruthenium precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on silica supports, formed uniform
Slurry；
Step 4: by slurry aging described in step 3 under conditions of temperature is 35 DEG C, stirring rate is 1000r/min
30h, the hydroxide ruthenium are anchored on the surface of powdered silica carrier, then using formic acid and sodium formate (mass ratio 3:
2) at ruthenium, product is added to centrifuge after the completion and is filtered and washed to nothing mixed liquor reduction hydroxide ruthenium by reduction reaction
Chloride ion obtains high dispersive 5%Ru/SiO through 100 DEG C of dryings2Fine catalyst；The mixed liquor of the formic acid and sodium formate
Total addition level is 6 times of ruthenium content in ruthenium trichloride described in step 1.
Embodiment 6
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered ceramic carrier and deionized water are uniformly mixed to form suspension；Chloroplatinic acid be dissolved in from
In sub- water, aqueous phase solution is formed；
The mass percentage of powdered ceramic carrier is 12% in the suspension, chloroplatinic acid in the aqueous phase solution
Mass concentration is 0.16g/mL；The mass content of platinum is the 2% of the powdered ceramic carrier quality in the chloroplatinic acid；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium carbonate and sodium carbonate adjust suspension is 9.8；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and platinum ion is under alkaline condition with platinic hydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on ceramic monolith, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 55 DEG C, stirring rate is 1000r/min
25h, the platinic hydroxide are anchored on the surface of powdered ceramic carrier, then using formic acid reduction platinic hydroxide at platinum, reduction
Product is added to plate and frame filter press after the reaction was completed to be filtered and washed to no chloride ion, after 80 DEG C dry, obtains height
Disperse 2%Pt/ ceramic powders catalyst；The additive amount of the formic acid is 3 times of platinum content in chloroplatinic acid described in step 1.
Embodiment 7
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 10% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.05g/mL；The mass content of palladium is the powdered active carbon carrier quality in the palladium chloride
0.01%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 9；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 55 DEG C, stirring rate is 1000r/min
15h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using formaldehyde reduction palladium dydroxide at palladium, also
Product is added to centrifuge after the reaction was completed and is filtered and washed to no chloride ion by original, obtains high dispersive 0.01%Pd/C powder
Last catalyst, moisture content 55%；The additive amount of the formaldehyde is 8 times of palladium content in palladium chloride described in step 1.
Embodiment 8
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered molecular sieve carrier and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powdered molecular sieve carrier is 45% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.01g/mL；The mass content of palladium is the 5% of the powdered molecular sieve carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that potassium hydroxide adjusts suspension is 8.5；
Step 3: being the atomization of 3um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on molecular sieve carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 45 DEG C, stirring rate is 1000r/min
For 24 hours, the palladium dydroxide is anchored on the surface of powdered molecular sieve carrier, then using sodium borohydride reduction palladium dydroxide at
Product is added to plate and frame filter press after the completion and is filtered and washed to no chloride ion by palladium, reduction reaction, after 85 DEG C are dry,
Obtain high dispersive 5%Pd/ molecular sieve powder catalyst；The additive amount of the sodium borohydride is palladium in palladium chloride described in step 1
5 times of content.
Embodiment 9
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered barium sulfate carrier and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powdered barium sulfate carrier is 5% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.15g/mL；The mass content of palladium is the 5% of the powdered barium sulfate carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 8.8；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on barium sulfate carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
20h, the palladium dydroxide are anchored on the surface of powdered barium sulfate carrier, then using formaldehyde reduction palladium dydroxide at palladium, also
Product is added to plate and frame filter press after the reaction was completed and is filtered and washed to no chloride ion by original, after 100 DEG C dry, is obtained
High dispersive 5%Pd/BaSO4Fine catalyst；The additive amount of the formaldehyde is 4 of palladium content in palladium chloride described in step 1
Times.
Embodiment 10
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: whiting carrier and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of whiting carrier is 12.5% in the suspension, chlorination in the aqueous phase solution
The mass concentration of palladium is 0.20g/mL；The mass content of palladium is the whiting carrier quality in the palladium chloride
3%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 7.5；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on calcium carbonate carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
1h, the palladium dydroxide are anchored on the surface of whiting carrier, then using hydrazine hydrate reduction palladium dydroxide at palladium, also
Product is added to negative pressure funnel after the reaction was completed and is filtered and washed to no chloride ion by original, after 85 DEG C dry, obtains height
Disperse 5%Pd/CaCO3Fine catalyst；The additive amount of the hydrazine hydrate is 6 of palladium content in palladium chloride described in step 1
Times.
Embodiment 11
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 20% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.01g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 9.0；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
18h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using hydrazine hydrate reduction palladium dydroxide at palladium,
Product is added to centrifuge after the completion of reduction reaction to be filtered and washed to no chloride ion, obtains high dispersive 5%Pd/C powder
Last catalyst, moisture content 65%；The additive amount of the hydrazine hydrate is 4 times of palladium content in palladium chloride described in step 1.
Fig. 1 is the SEM photograph of high dispersive 5%Pd/C catalyst manufactured in the present embodiment, be can be seen from the chart, palladium particle
High uniformity is dispersed on the outer surface of active carbon.
Embodiment 12
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 15% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.10g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide and potassium hydroxide (mass ratio 1:1) adjust suspension is 10.0；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 25 DEG C, stirring rate is 1000r/min
30h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using oxalic acid reduction palladium dydroxide at palladium, also
Product is added to centrifuge after the reaction was completed and is filtered and washed to no chloride ion by original, obtains high dispersive 5%Pd/C powder
Catalyst, moisture content 57%；The additive amount of the oxalic acid is 8 times of palladium content in palladium chloride described in step 1.
Embodiment 13
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 10% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.20g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 9.3；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
12h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using citric acid reduction palladium dydroxide at palladium,
Product is added to centrifuge after the completion of reduction reaction to be filtered and washed to no chloride ion, obtains high dispersive 5%Pd/C powder
Last catalyst, moisture content 55%；The additive amount of the citric acid is 7.5 times of palladium content in palladium chloride described in step 1.
Embodiment 14
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 30% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.15g/mL；The mass content of palladium is the powdered active carbon carrier quality in the palladium chloride
30%；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 8.5；
Step 3: being the atomization of 4um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
45h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using ascorbic acid reduction palladium dydroxide at
Product is added to centrifuge after the completion and is filtered and washed to no chloride ion by palladium, reduction reaction, obtains high dispersive 5%Pd/C
Fine catalyst, moisture content 48%；The additive amount of the ascorbic acid is 10 times of palladium content in palladium chloride described in step 1.
Embodiment 15
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 25% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.12g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 9.0；
Step 3: being the atomization of 4um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
30h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using polyethylene glycol reduction palladium dydroxide at
Product is added to centrifuge after the completion and is filtered and washed to no chloride ion by palladium, reduction reaction, obtains high dispersive 5%Pd/C
Fine catalyst, moisture content 52%；The additive amount of the polyethylene glycol is 6 times of palladium content in palladium chloride described in step 1.
Embodiment 16
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 1% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.10g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 8.5；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 85 DEG C, stirring rate is 1000r/min
3h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then use hydrazine hydrochloride and hydrazine hydrate (mass ratio 7:3)
Palladium dydroxide is restored into palladium, product is added to centrifuge after the completion and be filtered and washed to no chloride ion, obtained by reduction reaction
To high dispersive 5%Pd/C fine catalyst, moisture content 63%；The total addition level of the hydrazine hydrochloride and hydrazine hydrate is in step 1
2 times of palladium content in the palladium chloride.
Embodiment 17
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Palladium chloride is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 15% in the suspension, palladium chloride in the aqueous phase solution
Mass concentration be 0.10g/mL；The mass content of palladium is the 5% of the powdered active carbon carrier quality in the palladium chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that the mixed solution of sodium hydroxide and ammonium hydroxide (mass ratio 3:7) adjusts suspension is 9.0；
Step 3: being the atomization of 2um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and palladium ion is under alkaline condition with palladium dydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 65 DEG C, stirring rate is 1000r/min
10h, the palladium dydroxide are anchored on the surface of powder activated high-area carbon, then using formaldehyde reduction palladium dydroxide at palladium, also
Product is added to centrifuge after the reaction was completed and is filtered and washed to no chloride ion by original, obtains high dispersive 5%Pd/C powder
Catalyst, moisture content 68%；The additive amount of the formaldehyde is 5 times of palladium content in palladium chloride described in step 1.
Fig. 2 is the TEM photo of high dispersive 5%Pd/C catalyst manufactured in the present embodiment, from figure 2 it can be seen that palladium grain
Son is highly dispersed on absorbent charcoal carrier, and the particle diameter distribution of particle is uniform, average grain diameter 8.2nm.
Embodiment 18
The present embodiment prepare the method for high-dispersion loading type noble metal powder catalyst the following steps are included:
Step 1: powdered ceramic carrier and deionized water are uniformly mixed to form suspension；Gold chloride be dissolved in from
In sub- water, aqueous phase solution is formed；
The mass percentage of powdered ceramic carrier is 5% in the suspension, gold chloride in the aqueous phase solution
Mass concentration is 0.10g/mL；Golden mass content is the 4% of the powdered ceramic carrier quality in the gold chloride；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 9.5；
Step 3: being the atomization of 1um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and gold ion is under alkaline condition with gold hydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on ceramic monolith, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 5 DEG C, stirring rate is 1000r/min
48h, the gold hydroxide are anchored on the surface of powdered ceramic carrier, then restore gold hydroxide Cheng Jin using citric acid, also
Product is added to centrifuge after the reaction was completed and is filtered and washed to no chloride ion by original, after 40 DEG C dry, obtains high score
Dissipate 5%Au/ ceramic catalyst；The additive amount of the citric acid is 10 times of gold content in gold chloride described in step 1.
Embodiment 19
The present embodiment prepare high-dispersion loading type it is expensive silver belong to fine catalyst method the following steps are included:
Step 1: powder activated high-area carbon and deionized water are uniformly mixed to form suspension；Silver nitrate is dissolved in
In ionized water, aqueous phase solution is formed；
The mass percentage of powder activated high-area carbon is 10% in the suspension, silver nitrate in the aqueous phase solution
Mass concentration be 0.15g/mL；Silver-colored mass content is the 4% of the powdered active carbon carrier quality in the silver nitrate；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, starting stirring, and it is added
The pH value that sodium hydroxide adjusts suspension is 10.0；
Step 3: being the atomization of 1um with partial size after aqueous phase solution described in step 1 is atomized by high-pressure fog mouth
Grain sprays into stirring autoclave slurry reactor, and silver ion is under alkaline condition with silver hydroxide precipitation form in the aqueous phase solution
It is precipitated, is rapidly dispersed into suspension under agitation, and adsorb the surface for being deposited on absorbent charcoal carrier, form uniform slurry
Material；
Step 4: by slurry aging described in step 3 under conditions of temperature is 0 DEG C, stirring rate is 1000r/min
40h, the silver hydroxide are anchored on the surface of powder activated high-area carbon, then restore silver hydroxide Cheng Yin using formaldehyde, also
Product is added to centrifuge after the reaction was completed and is filtered and washed to no chloride ion by original, obtains high dispersive 5%Ag/C catalysis
Agent, moisture content 58%；The additive amount of the formaldehyde is 8 times of silver content in silver nitrate described in step 1.
The high dispersive 5%Pd/C catalyst and commercially available Pd/C catalyst prepared using embodiment 11~17 is used for adjacent chlorine nitro
The selective catalytic hydrogenation of benzene reacts.The concrete operations of catalytic hydrogenation reaction are as follows: accurate weighing o-chloronitrobenzene 20.0g, and 5%
Pd/C catalyst 0.02g, anti-dechlorination auxiliary agent 0.04g are added sequentially in 100mL stainless steel autoclave, are sealed, are then filled
Enter nitrogen and replace 3 air, is re-filled with hydrogen and replaces 3 nitrogen, then heat to 90 DEG C, being filled with hydrogen to pressure value is
0.80MPa, starting stirring starts to react, until no longer inhaling hydrogen.After reaction, reaction solution is pipetted, laggard gas phase color is diluted
Spectrum analysis, area normalization method calculate each component content.High dispersive 5%Pd/C catalyst prepared by embodiment 11~17 is in adjacent chlorine nitre
Catalytic performance experimental result in base hydrogenation reaction, as shown in table 1.
The high dispersive 5%Pd/C catalyst and commercially available Pd/C catalyst of 1 embodiment 11~17 of table preparation are used for adjacent chlorine nitro
The catalytic performance experimental result of benzene catalytic hydrogenation reaction
| Catalyst number | O-chloronitrobenzene/% | O-chloraniline/% | Aniline/% |
| Embodiment 11 | 0.23% | 98.62% | 1.12% |
| Embodiment 12 | 0.28% | 99.02% | 0.66% |
| Embodiment 13 | 0.13% | 97.97% | 1.85% |
| Embodiment 14 | 0.46% | 98.49% | 1.02% |
| Embodiment 15 | 0.51% | 99.23% | 0.22% |
| Embodiment 16 | 0.26% | 97.70% | 2.01% |
| Embodiment 17 | 0.09% | 99.86% | 0.03% |
| Commercially available Pd/C catalyst | 0.47% | 95.68% | 3.87% |
It can be seen that the 5%Pd/C of the high dispersive obtained by the operation of embodiment 11~17 from the experimental result in table 1
Catalyst shown in o-chloronitrobenzene selective hydrogenation it is highly selective, target product yield be greater than 97%, up to
99.86%, dechlorination rate is only 3/10000ths, and the Pd/C catalyst compared to more commercially available halonitro reduction has and is more preferably catalyzed
Performance.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (9)
1. a kind of preparation method of high-dispersion loading type noble metal powder catalyst, which is characterized in that this method includes following step
It is rapid:
Step 1: water-insoluble powder carrier is uniformly mixed to form suspension with deionized water；By noble metal precursor body
It is dissolved in deionized water, forms aqueous phase solution；In the suspension mass percentage of powder carrier be 1%~
50%, the mass concentration of noble metal precursor body is 0.01g/mL~0.20g/mL in the aqueous phase solution；The noble metal precursor
The mass content of noble metal is the 5%~30% of the powder carrier quality in body；
Step 2: suspension described in step 1 is added in stirring autoclave slurry reactor, start to stir, and adjust suspension
PH value be alkalinity；
Step 3: aqueous phase solution described in step 1 to be added to the stirring autoclave equipped with alkaline suspension in step 2 after being atomized
In slurry reactor, the precious metal ion of the aqueous phase solution is precipitated in the form of precious metal precipitation object under alkaline condition,
It is rapidly dispersed into suspension under stirring condition, and adsorbs the surface for the powder carrier being deposited in the suspension, finally
Form uniform slurry；
Step 4: by the 1h~48h of slurry aging described in step 3 under conditions of temperature is 0 DEG C~100 DEG C, stirs, it is described
Precious metal precipitation object is anchored on powder carrier surface, is then reduced into precious metal precipitation object by wet chemistry reduction method expensive
Metal, filtering and washing, obtain high-dispersion loading type noble metal powder catalyst.
2. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
Carrier described in step 1 is aluminium oxide, calcium carbonate, active carbon, barium sulfate, titanium dioxide, silica, molecular sieve or ceramics.
3. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
Noble metal precursor body described in step 1 is water soluble compound, the Rh of the water soluble compound of Pt, the water soluble compound of Pd, Ru
Water soluble compound, the water soluble compound of Ir, the water soluble compound of Au and Ag one of water soluble compound or
It is two or more.
4. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
The mass content of noble metal is the 5%~10% of the powder carrier quality in noble metal precursor body described in step 1.
5. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
By in urea, ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and saleratus in step 2
At least one substance adjusts the pH value of suspension to alkalinity.
6. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
The pH value of suspension is adjusted in step 2 to 8~10.
7. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
Aqueous phase solution described in step 3 is spraying at atomizing particle by high-pressure fog mouth, high-pressure atomizer or ultrasonic atomizer, described
The partial size of atomizing particle is 0.5um~5um.
8. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
Reducing agent used in wet chemistry restoring method described in step 4 is citric acid, oxalic acid, formaldehyde, formic acid, hydrazine hydrate, hydroboration
One or more of sodium, potassium borohydride, hydrazine hydrochloride, ascorbic acid and polyalcohol, the additive amount of the reducing agent are step
2~10 times of noble metal mass content in noble metal precursor body described in rapid one.
9. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, which is characterized in that
It is filtered in step 4 by plate and frame filter press, centrifuge or negative pressure funnel.
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