CN106582620A - Method for preparing high-dispersion loaded-type noble-metal powder catalyst - Google Patents
Method for preparing high-dispersion loaded-type noble-metal powder catalyst Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
The invention discloses a method for preparing a high-dispersion loaded-type noble-metal powder catalyst. The method comprises the steps: (1) uniformly mixing powdery carriers with deionized water so as to form a suspension, and dissolving a noble metal precursor into deionized water so as to form an aqueous-phase solution; (2) adding the suspension into a stirring-vessel slurry reactor, carrying out stirring, and adjusting the pH value of the suspension to be alkaline; (3) atomizing the aqueous-phase solution, then, adding the atomized aqueous-phase solution into the stirring-vessel slurry reactor, precipitating noble metal ions in the form of noble metal precipitates, and enabling the precipitates to be adsorbed and deposited to surfaces of the powdery carriers in the suspension, so as to form uniform slurry; and (4) subjecting the slurry to stirring and aging at a certain temperature, anchoring the noble metal precipitates to the surfaces of the powdery carriers, then, carrying out reduction on the noble metal precipitates, and carrying out filtering and washing, thereby obtaining the high-dispersion loaded-type noble-metal powder catalyst. According to the method, the preparation process is simple and is easy to control, so that the method is suitable for industrially producing the high-dispersion loaded-type noble-metal powder catalyst.
Description
Technical field
The invention belongs to catalysis material technical field, and in particular to a kind of high-dispersion loading type noble metal powder catalyst
Preparation method.
Background technology
High-dispersion loading type noble metal powder catalyst has high, selective good, service life cycle length of catalysis activity etc.
Feature, is extensively used in fields such as petrochemical industry, pharmacy, fine chemistry industry and organic syntheses, is had a very important role.From
German E. Jacobs in 1875 receive the conspicuous First that establishes and produce the contact subtraction unit of oleum in Creutz, and manufacture
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 that a class is wide
The reaction such as the environmental friendly catalysis material of general application, PARA FORMALDEHYDE PRILLS(91,95) low-temperature catalytic burning has good catalytic effect, and in ammino
Eliminate into reaction, organic pollution, hydrogenation and the aspect such as Reforming catalyst reaction, gas sensor, fuel cell have potential or real
Border using value.
At present, in the preparation and production process of high-dispersion load noble metal powder catalyst, there are various production methods, it is such as heavy
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 into fluidisation
On the activated carbon through soda acid process with oxidation processes in bed, hydrogen reducing is passed through, finally uses pure water.But the preparation side
Powdered active carbon is kept fluidized state by method by air-introduced machine in fluid bed, on the one hand inevitably results in powder activity
Charcoal sprays fluid bed with flow of warm nitrogen gas, more seriously, causes activated carbon to move at random in fluid bed, with palladium bichloride
The contact probability of solution is unequal, so as to cause active component palladium in the uneven distribution of activated carbon surface, and powder activity
After the adsorbing chlorinated palladium solution of charcoal, it is easy to tacky viscous wall, uneven dispersion of the palladium bichloride in activated carbon is further exacerbated by, has been catalyzed
Activity is difficult to be not fully exerted.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided a kind of high dispersive is born
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
Dust carrier surface is highly homogeneously dispersed in, the preparation efficiency and effect of carried noble metal fine catalyst is effectively improved
Really, the Active components distribution for solving carried noble metal fine catalyst prepared by production method of the prior art is uneven
It is even, easily reunite, the technical problem such as industrialization difficulty is big.
To solve above-mentioned technical problem, the technical solution used in the present invention is：A kind of high-dispersion loading type noble metal powder
The preparation method of catalyst, it is characterised in that the method is comprised the following steps：
Step one, non-water-soluble powder carrier is well mixed to form suspension with deionized water；Before noble metal
Drive body to be dissolved in deionized water, form aqueous phase solution；In the suspension weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and adjusted outstanding
The pH value of turbid liquid is alkalescence；
Step 3, aqueous phase solution described in step one is added in step 2 equipped with the stirring of alkaline suspension Jing after atomization
In autoclave slurry reactor, the precious metal ion of the aqueous phase solution is analysed in the basic conditions in the form of precious metal precipitation thing
Go out, be rapidly dispersed under agitation in suspension, and absorption is deposited on the surface of the powder carrier in the suspension,
Eventually form uniform slurry；
Step 4, temperature be 0 DEG C～100 DEG C, stirring under conditions of slurry described in step 3 is carried out aging 1h～
48h, the precious metal precipitation thing is anchored on powder carrier surface, then by wet chemistry reducing process by precious metal precipitation thing
Noble metal is reduced into, is filtered and is washed, obtain high-dispersion loading type noble metal powder catalyst.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, it is characterised in that institute in step one
Carrier is stated for aluminum oxide, calcium carbonate, activated 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, it is characterised in that described in step one
Noble metal precursor body is water soluble compound, the water soluble compound of Pd, the water soluble compound of Ru, the water solubilityization of Rh of Pt
One or more in the water soluble compound of compound, the water soluble compound of Ir, the water soluble compound of Au and Ag.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, it is characterised in that institute in step one
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, it is characterised in that institute in step one
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, it is characterised in that lead in step 2
At least one thing crossed in urea, ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus
Matter is adjusting the pH value of suspension to alkalescence.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, it is characterised in that adjust in step 2
The pH value of section suspension is to 8～10.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, it is characterised in that institute in step 3
State aqueous phase solution and atomizing particle is sprayed into by high-pressure fog mouth, high-pressure atomizer or ultrasonic atomizer, the atomizing particle
Particle diameter is 0.5um～5um.
A kind of preparation method of above-mentioned high-dispersion loading type noble metal powder catalyst, it is characterised in that institute in step 4
It is citric acid, oxalic acid, formaldehyde, formic acid, hydrazine hydrate, sodium borohydride, hydroboration to state the reducing agent used by wet chemistry method of reducing
One or more in potassium, hydrazine hydrochloride, ascorbic acid and polyalcohol, the addition of the reducing agent is described in step one
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, it is characterised in that lead in step 4
Cross plate and frame filter press, centrifuge or negative pressure funnel to be filtered.
The preparation method of above-mentioned a kind of high-dispersion loading type noble metal powder catalyst, it is characterised in that lead in step 4
Cross plate and frame filter press, centrifuge and negative pressure funnel to be filtered.
The present invention has compared with prior art advantages below：
1st, perform in the preparation method that the present invention is provided and spray atomization is adopted in precipitation deposition step by noble metal active group
Divide presoma aqueous phase solution and stirring autoclave slurry reactor is added to atomizing type, realize 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 for improving with active material, therefore while catalyst preparation efficiency is lifted, protect
The precipitation deposition effect of catalyst carrier is demonstrate,proved.In addition, the feed postition effective control precious metal ion of spray atomization with it is suspended
The combination of the 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 precipitation deposition step.
2nd, the present invention is atomized noble metal to dust carrier surface, dramatically in stirring autoclave slurry reactor
Equably it is highly dispersed on dust carrier surface, gives full play to noble metal as the effect of active component, improves product
Performance and uniformity, and the preparation method of the present invention, simple process, process operation is easily controllable, with high practicality,
Be conducive to industrialized production.
3rd, the preparation method of high-dispersion loading type noble metal powder catalyst of the invention, simple process, it is easy to operation control
System, can produce high-dispersion loading type noble metal powder catalyst, and noble metal active component is highly dispersed at carrier surface, has
High catalytic activity and selectivity.
Technical scheme is described in further detail below by drawings and Examples.
Description of the drawings
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 photos of agent.
Specific embodiment
Embodiment 1
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powdered alumina carrier and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition 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 bichloride
1%；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.2 that sodium carbonate adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure atomizer atomization after, the atomization with particle diameter as 3um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of alumina support, forms uniform slurry
Material；
Step 4, temperature be 50 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
24h, the palladium dydroxide is anchored on the surface of powdered alumina carrier, then using sodium borohydride reduction palladium dydroxide, also
Product is added to into negative pressure funnel after the completion of original reaction to be filtered and washed to without chlorion, is then dried at 100 DEG C, obtained
High dispersive 1%Pd/Al2O3Fine catalyst；The addition of the sodium borohydride is palladium content in palladium bichloride described in step one
2.5 again.
Embodiment 2
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder titania support and deionized water are uniformly mixed to form into suspension；Potassium chloroplatinate dissolves
In deionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder 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 powder TiO 2 carrying physique in the potassium chloroplatinate
The 5% of amount；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.5 that potassium carbonate adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and platinum ion is in the basic conditions with platinic hydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of titania support, forms uniform
Slurry；
Step 4, temperature be 85 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
18h, the platinic hydroxide is anchored on the surface of powder titania support, then using potassium borohydride reduction palladium dydroxide,
Product is added to into centrifuge after the completion of reduction reaction to be filtered and washed to without chlorion, it is then dry at 100 DEG C, obtain
To high dispersive 5%Pt/TiO2Fine catalyst；The addition of the sodium borohydride is that palladium contains in potassium chloroplatinate described in step one
4 times of amount.
Embodiment 3
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Rhodium chloride is dissolved in
In deionized water, aqueous phase solution is formed；
The weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.8 that potassium carbonate adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by ultrasonic atomizer atomization after, the atomization with particle diameter as 3um
Grain is sprayed in stirring autoclave slurry reactor, and rhodium ion is in the basic conditions with rhodium hydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 100 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is old
Change 24h, the rhodium hydroxide is anchored on the surface of powder activated high-area carbon, then palladium dydroxide, reduction are reduced using formaldehyde
Product is added to into centrifuge after the completion of reaction filtered and washed to without chlorion, obtaining high dispersive 10%Rh/C powder and urged
Agent, moisture content 58%；The addition of the formaldehyde is described in step one 10 times of rhodium content in rhodium chloride.
Embodiment 4
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Iridous chloride is dissolved in
In deionized water, aqueous phase solution is formed；
The weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.8 that potassium carbonate adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 3um
Grain is sprayed in stirring autoclave slurry reactor, and iridium ion is in the basic conditions with hydroxide iridium precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 100 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is old
Change 48h, the hydroxide iridium is anchored on the surface of powder activated high-area carbon, then using potassium borohydride reduction hydroxide iridium,
Product is added to into centrifuge after the completion of reduction reaction to be filtered and washed to without chlorion, obtaining high dispersive 3%Ir/C powder
Last catalyst, moisture content 65%；The addition of the sodium borohydride is described in step one 10 times of iridium content in iridous chloride.
Embodiment 5
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powdered silica carrier and deionized water are uniformly mixed to form into suspension；Ruthenium trichloride dissolves
In deionized water, aqueous phase solution is formed；
The weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 7.8 that potassium carbonate and sodium carbonate adjust the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 3um
Grain is sprayed in stirring autoclave slurry reactor, and ruthenium ion is in the basic conditions with hydroxide ruthenium precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of silica supports, forms uniform
Slurry；
Step 4, temperature be 35 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
30h, the hydroxide ruthenium is anchored on the surface of powdered silica carrier, then using formic acid and sodium formate (mass ratio 3:
2) mixed liquor reduces hydroxide ruthenium into ruthenium, product is added to into centrifuge after the completion of reduction reaction and is filtered and is washed to nothing
Chlorion, 100 DEG C of dryings of Jing, obtains high dispersive 5%Ru/SiO2Fine catalyst；The mixed liquor of the formic acid and sodium formate
Total addition level is described in step one 6 times of ruthenium content in ruthenium trichloride.
Embodiment 6
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powdered ceramic carrier and deionized water are uniformly mixed to form into suspension；Chloroplatinic acid be dissolved in from
In sub- water, aqueous phase solution is formed；
The weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.8 that potassium carbonate and sodium carbonate adjust the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and platinum ion is in the basic conditions with platinic hydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of ceramic monolith, forms uniform slurry
Material；
Step 4, temperature be 55 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
25h, the platinic hydroxide is anchored on the surface of powdered ceramic carrier, then reduces platinic hydroxide into platinum, reduction using formic acid
Product is added to into plate and frame filter press after the completion of reaction to be filtered and washed to without chlorion, Jing after 80 DEG C of dryings, height is obtained
Dispersion 2%Pt/ ceramic powders catalyst；The addition of the formic acid is described in step one 3 times of platinum content in chloroplatinic acid.
Embodiment 7
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 10% in the suspension, palladium bichloride 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 bichloride
0.01%；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 55 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
15h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then reduces palladium dydroxide into palladium using formaldehyde, also
Product is added to into centrifuge after the completion of original reaction to be filtered and washed to without chlorion, obtaining high dispersive 0.01%Pd/C powder
Last catalyst, moisture content 55%；The addition of the formaldehyde is described in step one 8 times of palladium content in palladium bichloride.
Embodiment 8
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powdered molecular sieve carrier and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powdered molecular sieve carrier is 45% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.5 that potassium hydroxide adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 3um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of molecular sieve carrier, forms uniform slurry
Material；
Step 4, temperature be 45 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
24h, the palladium dydroxide is anchored on the surface of powdered molecular sieve carrier, then using sodium borohydride reduction palladium dydroxide into
Palladium, is added to plate and frame filter press and is filtered and washed to without chlorion after the completion of reduction reaction by product, Jing after 85 DEG C of dryings,
Obtain high dispersive 5%Pd/ molecular sieve powder catalyst；The addition of the sodium borohydride is palladium in palladium bichloride described in step one
5 times of content.
Embodiment 9
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder barium sulfate carrier and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder barium sulfate carrier is 5% in the suspension, palladium bichloride in the aqueous phase solution
Mass concentration be 0.15g/mL；The mass content of palladium is the 5% of the powder barium sulfate carrier quality in the palladium bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.8 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of barium sulfate carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
20h, the palladium dydroxide is anchored on the surface of powder barium sulfate carrier, then reduces palladium dydroxide into palladium using formaldehyde, also
Product is added to into plate and frame filter press after the completion of original reaction to be filtered and washed to without chlorion, Jing after 100 DEG C of dryings, is obtained
High dispersive 5%Pd/BaSO4Fine catalyst；The addition of the formaldehyde is 4 of palladium content in palladium bichloride described in step one
Times.
Embodiment 10
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, whiting carrier and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition 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 bichloride
3%；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 7.5 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of calcium carbonate carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
1h, the palladium dydroxide is anchored on the surface of whiting carrier, then using hydrazine hydrate reduction palladium dydroxide into palladium, also
Product is added to into negative pressure funnel after the completion of original reaction to be filtered and washed to without chlorion, Jing after 85 DEG C of dryings, height is obtained
Dispersion 5%Pd/CaCO3Fine catalyst；The addition of the hydrazine hydrate is 6 of palladium content in palladium bichloride described in step one
Times.
Embodiment 11
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 20% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.0 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
18h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then using hydrazine hydrate reduction palladium dydroxide into palladium,
Product is added to into centrifuge after the completion of reduction reaction to be filtered and washed to without chlorion, obtaining high dispersive 5%Pd/C powder
Last catalyst, moisture content is 65%；The addition of the hydrazine hydrate is described in step one 4 times of palladium content in palladium bichloride.
Fig. 1 is the SEM photograph of high dispersive 5%Pd/C catalyst manufactured in the present embodiment, from figure as can be seen that palladium particle
High uniformity is dispersed on the outer surface of activated carbon.
Embodiment 12
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 15% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
NaOH and potassium hydroxide (mass ratio 1:1) pH value for adjusting suspension is 10.0；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 25 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
30h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then reduces palladium dydroxide into palladium using oxalic acid, also
Product is added to into centrifuge after the completion of original reaction to be filtered and washed to without chlorion, obtaining high dispersive 5%Pd/C powder
Catalyst, moisture content is 57%；The addition of the oxalic acid is described in step one 8 times of palladium content in palladium bichloride.
Embodiment 13
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 10% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.3 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
12h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then reduces palladium dydroxide into palladium using citric acid,
Product is added to into centrifuge after the completion of reduction reaction to be filtered and washed to without chlorion, obtaining high dispersive 5%Pd/C powder
Last catalyst, moisture content is 55%；The addition of the citric acid is described in step one 7.5 times of palladium content in palladium bichloride.
Embodiment 14
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 30% in the suspension, palladium bichloride 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 bichloride
30%；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.5 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 4um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
45h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then using ascorbic acid reduce palladium dydroxide into
Palladium, is added to centrifuge and is filtered and washed to without chlorion after the completion of reduction reaction by product, obtains high dispersive 5%Pd/C
Fine catalyst, moisture content 48%；The addition of the ascorbic acid is described in step one 10 times of palladium content in palladium bichloride.
Embodiment 15
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 25% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.0 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 4um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
30h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then using polyethylene glycol reduce palladium dydroxide into
Palladium, is added to centrifuge and is filtered and washed to without chlorion after the completion of reduction reaction by product, obtains high dispersive 5%Pd/C
Fine catalyst, moisture content 52%；The addition of the polyethylene glycol is described in step one 6 times of palladium content in palladium bichloride.
Embodiment 16
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 1% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 8.5 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 85 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
3h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then using hydrazine hydrochloride and hydrazine hydrate (mass ratio 7：3)
Product is added to centrifuge and is filtered and washed to without chlorion by reduction palladium dydroxide into palladium after the completion of reduction reaction, is obtained
To high dispersive 5%Pd/C fine catalyst, moisture content is 63%；The total addition level of the hydrazine hydrochloride and hydrazine hydrate is in step one
2 times of palladium content in the palladium bichloride.
Embodiment 17
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Palladium bichloride is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 15% in the suspension, palladium bichloride 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 bichloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
NaOH and ammoniacal liquor (mass ratio 3:7) it is 9.0 that mixed solution adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 2um
Grain is sprayed in stirring autoclave slurry reactor, and palladium ion is in the basic conditions with palladium dydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 65 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
10h, the palladium dydroxide is anchored on the surface of powder activated high-area carbon, then reduces palladium dydroxide into palladium using formaldehyde, also
Product is added to into centrifuge after the completion of original reaction to be filtered and washed to without chlorion, obtaining high dispersive 5%Pd/C powder
Catalyst, moisture content is 68%；The addition of the formaldehyde is described in step one 5 times of palladium content in palladium bichloride.
Fig. 2 is the TEM photos 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 even particle size distribution of particle, average grain diameter is 8.2nm.
Embodiment 18
The present embodiment prepares the method for high-dispersion loading type noble metal powder catalyst and comprises the following steps：
Step one, powdered ceramic carrier and deionized water are uniformly mixed to form into suspension；Gold chloride be dissolved in from
In sub- water, aqueous phase solution is formed；
The weight/mass percentage composition of powdered ceramic carrier is 5% in the suspension, gold chloride in the aqueous phase solution
Mass concentration is 0.10g/mL；The mass content of gold is the 4% of the powdered ceramic carrier quality in the gold chloride；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 9.5 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 1um
Grain is sprayed in stirring autoclave slurry reactor, and gold ion is in the basic conditions with gold hydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of ceramic monolith, forms uniform slurry
Material；
Step 4, temperature be 5 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
48h, the gold hydroxide is anchored on the surface of powdered ceramic carrier, then reduces gold hydroxide Cheng Jin using citric acid, also
Product is added to into centrifuge after the completion of original reaction to be filtered and washed to without chlorion, Jing after 40 DEG C of dryings, high score is obtained
Scattered 5%Au/ ceramic catalysts；The addition of the citric acid is described in step one 10 times of gold content in gold chloride.
Embodiment 19
The present embodiment prepares the method for the expensive silver category fine catalyst of high-dispersion loading type and comprises the following steps：
Step one, powder activated high-area carbon and deionized water are uniformly mixed to form into suspension；Silver nitrate is dissolved in
In ionized water, aqueous phase solution is formed；
The weight/mass percentage composition of powder activated high-area carbon is 10% in the suspension, silver nitrate in the aqueous phase solution
Mass concentration be 0.15g/mL；The mass content of silver is the 4% of the powdered active carbon carrier quality in the silver nitrate；
Step 2, suspension described in step one is added in stirring autoclave slurry reactor, starts stirring, and added
It is 10.0 that NaOH adjusts the pH value of suspension；
Step 3, by aqueous phase solution described in step one by high-pressure fog mouth atomization after, the atomization with particle diameter as 1um
Grain is sprayed in stirring autoclave slurry reactor, and silver ion is in the basic conditions with silver hydroxide precipitation form in the aqueous phase solution
Separate out, be rapidly dispersed in suspension under agitation, and absorption is deposited on the surface of absorbent charcoal carrier, forms uniform slurry
Material；
Step 4, temperature be 0 DEG C, stir speed (S.S.) be 1000r/min under conditions of slurry described in step 3 is aging
40h, the silver hydroxide is anchored on the surface of powder activated high-area carbon, then reduces silver hydroxide Cheng Yin using formaldehyde, also
Original reaction after the completion of by product be added to centrifuge filtered and washed to without chlorion, obtain high dispersive 5%Ag/C catalysis
Agent, moisture content is 58%；The addition of the formaldehyde is described in step one 8 times of silver content in silver nitrate.
The high dispersive 5%Pd/C catalyst prepared using embodiment 11～17 and commercially available Pd/C catalyst are used for adjacent chlorine nitro
The selective catalytic hydrogenation reaction of benzene.The concrete operations of catalytic hydrogenation reaction are as follows：Accurate weighing o-chloronitrobenzene 20.0g, 5%
Pd/C catalyst 0.02g, anti-dechlorination auxiliary agent 0.04g, in being added sequentially to 100mL stainless steel autoclaves, sealing, Ran Houchong
Enter 3 air of nitrogen displacement, be re-filled with 3 nitrogen of hydrogen exchange, then heat to 90 DEG C, be filled with hydrogen is to pressure value
0.80MPa, starts stirring and starts reaction, to no longer hydrogen is inhaled.After reaction terminates, reactant liquor is pipetted, dilute laggard gas phase color
Analysis of spectrum, area normalization method calculates 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.
High dispersive 5%Pd/C catalyst and commercially available Pd/C catalyst prepared by 1 embodiment of table 11～17 is used for adjacent chlorine nitro
The catalytic performance experimental result of benzene catalytic hydrogenation reaction
| Catalyst is numbered | 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% |
Experimental result from table 1 can be seen that the 5%Pd/C of the high dispersive obtained by the operation of embodiment 11～17
Catalyst shows high selectivity in o-chloronitrobenzene selective hydrogenation, and target product yield is more than 97%, up to
99.86%, dechlorination rate is only 3/10000ths, and the Pd/C catalyst for comparing more commercially available halonitro reduction has more excellent catalysis
Performance.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence changes that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. a kind of preparation method of high-dispersion loading type noble metal powder catalyst, it is characterised in that the method includes following step
Suddenly：
Step one, non-water-soluble powder carrier is well mixed to form suspension with deionized water；By noble metal precursor body
In being dissolved in deionized water, aqueous phase solution is formed；In the suspension weight/mass percentage composition 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 one is added in stirring autoclave slurry reactor, starts stirring, and adjust suspension
PH value for alkalescence；
Step 3, aqueous phase solution described in step one is added in step 2 equipped with the stirring autoclave of alkaline suspension Jing after atomization
In slurry reactor, the precious metal ion of the aqueous phase solution is separated out in the basic conditions in the form of precious metal precipitation thing,
It is rapidly dispersed under stirring condition in suspension, and absorption is deposited on the surface of the powder carrier in the suspension, finally
Form uniform slurry；
Step 4, temperature be 0 DEG C～100 DEG C, under conditions of stirring by the aging 1h～48h of slurry described in step 3, it is described
Precious metal precipitation thing is anchored on powder carrier surface, is then reduced into precious metal precipitation thing by wet chemistry reducing process expensive
Metal, filters and washs, and obtains 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, it is characterised in that
Carrier described in step one is aluminum oxide, calcium carbonate, activated 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, it is characterised in that
Noble metal precursor body described in step one is water soluble compound, the water soluble compound of Pd, the water soluble compound of Ru, the Rh of Pt
Water soluble compound, the water soluble compound of Ir, the water soluble compound of the water soluble compound of Au and Ag in one kind 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, it is characterised in that
The mass content of noble metal is the 0.01%～30% of the powder carrier quality in noble metal precursor body described in step one.
5. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 4, it is characterised in that
The mass content of noble metal is the 1%～10% of the powder carrier quality in noble metal precursor body described in step one.
6. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, it is characterised in that
By in urea, ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus in step 2
At least one material is adjusting the pH value of suspension to alkalescence.
7. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, it is characterised in that
The pH value of suspension is adjusted in step 2 to 8～10.
8. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, it is characterised in that
Aqueous phase solution described in step 3 sprays into atomizing particle by high-pressure fog mouth, high-pressure atomizer or ultrasonic atomizer, described
The particle diameter of atomizing particle is 0.5um～5um.
9. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, it is characterised in that
Reducing agent used by wet chemistry method of reducing described in step 4 is citric acid, oxalic acid, formaldehyde, formic acid, hydrazine hydrate, hydroboration
One or more in sodium, potassium borohydride, hydrazine hydrochloride, ascorbic acid and polyalcohol, the addition of the reducing agent is step
Described in rapid one 2～10 times of noble metal mass content in noble metal precursor body.
10. a kind of preparation method of high-dispersion loading type noble metal powder catalyst according to claim 1, its feature exists
In being filtered by plate and frame filter press, centrifuge or negative pressure funnel in step 4.
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| CN109046342A (en) * | 2018-07-13 | 2018-12-21 | 南京卡邦科技有限公司 | A kind of preparation method of nanocatalyst |
| CN110026211A (en) * | 2019-05-14 | 2019-07-19 | 山东师范大学 | A kind of heterojunction composite and preparation method and application |
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| CN113929114A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Method and system for recovering ammonia from nitrile-containing organic wastewater |
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