CN108067220A - A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application - Google Patents
A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application Download PDFInfo
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- CN108067220A CN108067220A CN201610988433.1A CN201610988433A CN108067220A CN 108067220 A CN108067220 A CN 108067220A CN 201610988433 A CN201610988433 A CN 201610988433A CN 108067220 A CN108067220 A CN 108067220A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
Abstract
The present invention provides a kind of hydrogen peroxide synthesis loaded catalysts and its preparation method and application.The catalyst activity component is Metal Palladium, and catalyst carrier is acid carrier；The loading of palladium is 0.1% 20%, and the catalyst is using precious metals pd as active component, Supported oxide, molecular sieve, on carbon material carrier.The palladium that the present invention loads can uniformly be distributed in the surface of catalyst carrier, particle size can be with Effective Regulation, interaction can effectively improve the synthesis of hydrogen peroxide between carrier and catalyst activity component, the dosage of noble metal can be reduced using this method, a large amount of generations of by-product are avoided, and then improve the selectivity of catalyst.
Description
Technical field
The invention belongs to petrochemical industries, and in particular to a kind of hydrogen peroxide synthesis loaded catalyst and its preparation side
Method further relates to its application in hydrogen-oxygen directly synthesizes hydrogen peroxide reaction.
Background technology
Hydrogen peroxide is a kind of important inorganic chemical, can be used as oxidant, disinfectant, bleaching agent, deoxidier etc., quilt
It is widely used in the industries such as papermaking, chemical industry, environmental protection, electronics, space flight.Hydrogen peroxide is as Green Oxidant, the product after use
For water and oxygen, thus it is environmentally safe.It is a kind of green chemical.In recent years, it is double in new green chemical industry field
Oxygen water is widely used in the production of the products such as caprolactam, cyclohexanone, hydroquinone, propylene oxide as green chemical.
The application of exactly hydrogen peroxide increases, and the yield of hydrogen peroxide increases year by year, and Hydrogen Peroxide Industry has also obtained long-range development.Mesh
Before, global hydrogen peroxide total productive capacity has reached 22,000,000 tons/year, and hydrogen peroxide manufacture ability is with annual 8%
~11% speed increases.At the same time, the Hydrogen Peroxide Industry development in China is similary rapid, and the hydrogen peroxide market demand is continuous
Expand, production capacity also steps up, 2015, and the country produces hydrogen peroxide per year up to 1,700,000 tons (with 100%H2O2Meter).Peroxidating
Hydrogen production method has electrolysis, anthraquinone and hydrogen-oxygen direct synthesis technique, wherein anthraquinone is the method being most widely used.Anthraquinone
The process of method production hydrogen peroxide mainly includes hydrogenation process and oxidation process, and hydrogen peroxide obtains after extract and separate, simultaneously
Anthraquinone can be recycled.But anthraquinone there is the shortcomings that apparent：Using organic solvent, there is hydrogen, oxygen, double in the process
Oxygen water and organic solvent coexist, and certain danger is brought to production.
Compared with tradition is anthraquinone, hydrogen peroxide new process is directly synthesized by hydrogen, oxygen and is had a clear superiority, be a kind of preferable
Atom economy, the production method of green economy, therefore, it is considered to be a hydrogen peroxide technological revolution.Domestic and foreign scholars to this into
Extensive research is gone, mainly including active component, catalyst carrier composition, composition of reaction solution etc..
Wang Shu east et al. is with one or two kinds of for active component in precious metals pd, Pt, coated on molecular sieve-oxide
Meet and integral catalyzer is made on carrier, be conducive to the stability of catalyst, but method for preparing catalyst is simple, catalyst
Granular size is uncontrollable (CN104368374A).And in another patent, Wang Shudong et al. answers the components such as group of the lanthanides and titanium, nickel
It closes, the synthesis (CN101433843A) of anthraquinone hydrogen peroxide is used for after shaping.Guo Hong ministers et al. were synthesized with plasma method
Hydrogen oxide is discharged by DBD, can continuously produce hydrogen peroxide, and the apparatus structure is simple, but high caused by electrion
Energy consumption and safety problem can not look down upon (CN103435014B).Cao Yong et al. substitutes palladium-based catalyst for double with copper-based catalysts
The synthesis of oxygen water, at this time the composition of reaction gas also become carbon monoxide, oxygen gas and water, cause catalytic reaction activity and selectivity
Relatively low (CN100457259C).Hydrogen and oxygen directly synthesizes usually adds in acid and halogen during hydrogen peroxide, inhibits double with this
The decomposition of oxygen water and excessive hydrogenation.The patent report directly modifies catalyst carrier acidic-group and halogen group, carrier
In there is the acidic-groups such as sulfonic group and halogen group simultaneously, therefore reduce the halogen in reaction solution and acidic materials, reach
Simplified technique, the purpose CN103717304A of green production, but the acidity of the catalyst is relatively low, and production efficiency is relatively low.
Lunsford et al. has investigated influence of the valence state to hydrogen peroxide of palladium, specially discusses direct by hydrogen and oxygen
Form the Pd/SiO in hydrogen peroxide2、PdO/SiO2With the PdO/SiO of partial reduction2Catalysis behavior
(Catal.Lett.2009,132,342-348)。
Strukul et al. has then been investigated and has been carried on SO4 2-、Cl-、F-And Br-Palladium catalyst on the zirconium oxide of doping is used for
The synthesis (Journal of Catalysis, 239,2006,422-430) of hydrogen peroxide, author thinks the Pd of surface oxidation0Catalysis
High catalytic activity and highest selectivity are shown in agent.Yamashita et al. is proposed to be carried in its net structure
SO3The acidic resins of H functional groups serve as to be responsible for by hydrogen and the active Pd nano particles of oxygen producing hydrogen peroxide by direct synthesis
A kind of carrier (J.Phys.Chem.Lett.2010,1,1675-1678) being formed in situ.
According to existing patent and document, the load type palladium catalyst for preparing high dispersive directly synthesizes hydrogen peroxide for hydrogen-oxygen
Synthesis is favourable, and the selectivity of hydrogen can be effectively improved by the size for regulating and controlling palladium metal, reduces the generation of side reaction.
Therefore, the present invention relates to a kind of simple effective methods of offer to prepare palladium-based catalyst, and is applied to directly synthesis peroxide
During changing hydrogen.
The content of the invention
High, active principle high dispersive, the catalyst of high catalytic efficiency the present invention provides a kind of noble metal utilisation.This is urged
Agent is prepared by colloid method, and simple synthetic method of the invention is easy, environmentally protective, safe and non-toxic, has wide development
Space and great market application value, more meet the requirement of sustainable development.
The present invention provides a kind of hydrogen peroxide synthesis loaded catalyst, and catalyst activity component is Metal Palladium, catalyst
Carrier is acid carrier；The loading of palladium is 0.1%-20%, is preferably 1%-5%.
Catalyst carrier includes oxide, molecular sieve, carbon material.
Oxide is in silica, aluminium oxide, titanium oxide, zirconium oxide, cerium oxide or lanthana in catalyst carrier
It is one or more kinds of；Molecular sieve is included more than one or both of ZSM-5, TS-1,5A, 4A or 13X；Carbon material includes carbon
It is more than one or both of nanotube, Nano carbon balls, carbon fiber or graphene.
Catalyst activity component is made of palladium, and the loading of palladium is 0.1%-10%, and the grain size of palladium is 0.5nm-15nm.
Catalyst of the present invention is prepared by colloid method.
Concrete operation step includes:By polyvinylpyrrolidone PVP and palladium salt, (molar ratio of PVP and palladium salt is 0.5:1~
50:1) be dissolved in water, then by above two solution be mixed 0.5-8 it is small when, weigh reducing agent (reducing agent and palladium salt
Ratio be 0.5:1~5:1), it is dissolved in ice water, the reducing agent solution of dissolving is disposably poured into polyvinylpyrrolidone
PVP protection palladium colloidal sol in, continue stir 0.5-5 it is small when, obtain colloidal sol, weigh catalyst carrier, be added in colloidal sol, pass through
Dust technology adjust colloidal sol pH, the pH value of solution is made to reach the isoelectric point of carrier, continue stir 0.5-6 it is small when after, use deionization
Catalyst detergent to neutrality, drying, roasting are obtained the loaded catalyst by water.
Drying temperature is 60-150 DEG C (in baking oven), when drying time is 10-24 small；Calcination temperature is 300-800 DEG C
(in Muffle furnace), when roasting time is 1-6 small.
Under conditions of polyvinylpyrrolidone protection, the mechanism for forming stable palladium particle is as follows:In a heated condition, cloth
Under the action of bright movement, convective motion, gravity and other power, palladium particle can be collided mutually, cause the reunion of colloid.But when poly-
After vinylpyrrolidone dissolving, the palladium nano-particles of preparation can be surrounded by polymer molecule, reduce touching between metallic particles
It hits, ensure that the stability of palladium nano-particles.
Polyvinylpyrrolidone concentration soluble in water is 5-20000ppm, and the molecular weight of polyvinylpyrrolidone PVP is
5000-100000, preferred molecular weight are 10000-30000；
Palladium salt concentration soluble in water is 10-20000ppm；Dust technology molar concentration be 0.01~2mol/l, reducing agent with
The molar ratio of palladium is 0.5~5.
The reducing agent includes sodium borohydride, citric acid, ascorbic acid；
Palladium salt includes nitrate, and chlorate, acetate, palladium salt is preferably palladium nitrate, palladium, palladium acetylacetonate, chlorination
Palladium.
The present invention also provides the loaded catalyst application in hydrogen peroxide reaction is directly synthesized in hydrogen-oxygen.Including by first
Alcohol mixes according to a certain percentage with certain density aqueous sulfuric acid, NaBr and certain mass catalyst is added in, in certain pressure
Hydrogen, react certain time under oxygen and argon gas mixed atmosphere.
The mass ratio of the reaction system each component is：
The volume ratio of methanol and aqueous sulfuric acid is 4:1~1:4, the concentration of sodium bromide is 0.001~1mol/L, the sulphur
Aqueous acid concentration is 0.2~4mol/L, and gas pressure is 0.5~10Mpa, and gas ratio of components is H2/O2/N2=1~5%:2
~20%:75~97%, the temperature of reaction is -5~40 DEG C, when the time of reaction is 10 minutes~10 small.
Beneficial effects of the present invention：
1. surfactant is the nonionic surface active agent of one or more mixtures.
2. the metallic colloid dispersed phase of surfactant protection is water, other organic solvents are not required to, avoid causing organic dirt
Dye, while reduce production cost.
3. the metallic colloid of surfactant protection is easily absorbing on carrier, carrier is not required to any pretreatment, load
Catalyst noble metal afterwards not easily runs off, and catalytic activity is high, long lifespan.
4. method for preparing catalyst is simple, reproducible, nano-metal particle is highly dispersed on carrier.
5. the filtrate after filtering can be recycled, the catalyst after inactivation can be loaded repeatedly.
The present invention prepares load type palladium catalyst by colloid method, and the metallic colloid of PVP protections is easy to load to carrier
On, and any pretreatment is not required in carrier, and the catalyst noble metal content after load is not lost in, suitable with theoretical content,
It thus provides a kind of noble metal utilisation is high, and active principle high dispersive, the method for preparing catalyst of high catalytic efficiency.This hair
Bright simple synthetic method is easy, reproducible, environmentally protective, safe and non-toxic, has wide development space and great city
Field application value, more meets the requirement of sustainable development.
Specific embodiment
Embodiment 1
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titania support is weighed, is added in colloidal sol, the pH value of colloidal sol is adjusted by dust technology
To 3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, 110 DEG C in an oven
It is dried overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 2
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of silica supports are weighed, are added in colloidal sol, the pH value of colloidal sol is adjusted by dust technology
To 3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, 110 DEG C in an oven
It is dried overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/SiO2。
Embodiment 3
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of activity carbon carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/C.
Embodiment 4
It weighs 4.172g (0.0375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 5
It weighs 0.04172g (0.000375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of activity carbon carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 6
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.03g
(0.0007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains TiO2。
Embodiment 7
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium bichloride 0.0666g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
5, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 8
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium acetylacetonate 0.11449g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 300 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 9
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 800 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 10
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.028g
(0.00015860mol) ascorbic acid is added in the palladium colloidal sol of PVP protections, at 80 DEG C, continues to stir 2h.Weigh titanium oxide load
4.1 grams of body, is added in colloidal sol, and after stirring 2h, obtained sample is washed to 3 for the pH value for adjusting colloidal sol by dust technology
It washs, with deionized water by catalyst detergent to neutrality, is dried overnight for 110 DEG C in an oven, finally by catalyst in Muffle furnace
800 DEG C of roasting 4h, obtain Pd/TiO2。
Embodiment 11
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.015g
(0.00007930mol) citric acid is dissolved in 5ml water, is added in the palladium colloidal sol of PVP protections, keeps 80 DEG C of stirring 2h.Claim
4.1 grams of titanium dioxide carrier is taken, is added in colloidal sol, by the pH value of dust technology adjusting colloidal sol to 3, after stirring 2h, by what is obtained
Sample is washed, and with deionized water by catalyst detergent to neutrality, is dried overnight for 110 DEG C in an oven, finally by catalyst
800 DEG C of roasting 4h, obtain Pd/TiO in Muffle furnace2。
Embodiment 12
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
7, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 800 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 13
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed in and stirs 2h under room temperature.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring for 24 hours, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 800 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 14
It weighs 0.4172g (0.00375856mol) PVP to be dissolved in 10ml water, then by palladium nitrate 0.0866g
(0.00037582mol) is dissolved in 40ml water, and above two solution is mixed under the conditions of 80 DEG C and stirs 2h.Weigh 0.003g
(0.00007930mol) sodium borohydride is dissolved in ice water, and the sodium borohydride solution of dissolving is disposably poured into the palladium of PVP protections
In colloidal sol, continue to stir 2h.4.1 grams of titanium dioxide carrier is weighed, is added in colloidal sol, the pH value that colloidal sol is adjusted by dust technology arrives
3, after stirring 2h, obtained sample is washed, with deionized water by catalyst detergent to neutrality, in an oven 110 DEG C it is dry
It is dry overnight, catalyst is finally roasted into 4h for 800 DEG C in Muffle furnace, obtains Pd/TiO2。
Embodiment 15
Weigh 20mg Pd/TiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa10%O2/N2Reaction kettle is maintained at 5 DEG C of water of constant temperature by gas
1h is kept in bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas after reaction is carried out by gas-chromatography
Analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 16
Weigh 20mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa10%O2/N2Reaction kettle is maintained at 5 DEG C of water of constant temperature by gas
1h is kept in bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas after reaction is carried out by gas-chromatography
Analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 17
Weigh 20mg Pd/TiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.1mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa10%O2/N2Reaction kettle is maintained at 5 DEG C of water of constant temperature by gas
1h is kept in bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas after reaction is carried out by gas-chromatography
Analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 18
Weigh 100mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa 10%O2/N2Reaction kettle is maintained at 5 DEG C of constant temperature by gas
1h is kept in water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.To the gas after reaction by gas-chromatography into
Row analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 19
Weigh 20mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 1%H2/N2Gas is finally filled with 2MPa10%O2/N2Reaction kettle is maintained at 5 DEG C of water of constant temperature by gas
1h is kept in bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas after reaction is carried out by gas-chromatography
Analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 20
Weigh 20mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 3mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 10%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa 10%O2/N2Reaction kettle is maintained at 5 DEG C of constant temperature by gas
1h is kept in water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.To the gas after reaction by gas-chromatography into
Row analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 21
Weigh 20mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 3MPa 6%H2/N2Gas is finally filled with 1MPa 10%O2/N2Reaction kettle is maintained at 50 DEG C of constant temperature by gas
1h is kept in water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.To the gas after reaction by gas-chromatography into
Row analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 22
Weigh 20mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 1mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 1MPa 6%H2/N2Gas is finally filled with 3MPa10%O2/N2Reaction kettle is maintained at 5 DEG C of water of constant temperature by gas
1h is kept in bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas after reaction is carried out by gas-chromatography
Analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 23
Weigh 0.1mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 5mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa 10%O2/N2Reaction kettle is maintained at 5 DEG C of constant temperature by gas
1h is kept in water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.To the gas after reaction by gas-chromatography into
Row analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 24
Weigh 0.1mg Pd/SiO2Catalyst adds in the isopropanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 5mol/l,
Simultaneously plus the NaBr solution that 100 μ l concentration are 0.01mol/l, first by 6%H2/N2It is filled in the reaction kettle of 100ml, replaces
Three times, 2MPa 6%H are then charged with2/N2Gas is finally filled with 2MPa 10%O2/N2Reaction kettle is maintained at constant temperature 5 by gas
1h is kept in DEG C water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.Gas-chromatography is passed through to the gas after reaction
It is analyzed, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Embodiment 25
Weigh 0.1mg Pd/SiO2Catalyst adds in the methanol of 20ml, and 5ml concentration is the dilution heat of sulfuric acid of 5mol/l, together
When plus 100 μ l concentration be 0.01mol/l NaBr solution, first by 6%H2/N2It is filled in the reaction kettle of 100ml, displacement three
It is secondary, it is then charged with 2MPa 6%H2/N2Gas is finally filled with 2MPa 10%O2/N2Reaction kettle is maintained at 5 DEG C of constant temperature by gas
1h is kept in water-bath, speed is kept stirring and opens mechanical agitator for 1500rpm.To the gas after reaction by gas-chromatography into
Row analysis, the content of hydrogen peroxide carries out quantitative analysis by cerimetry in solution after reaction, obtains the content of hydrogen peroxide.
Above-mentioned experiment catalyst in hydroperoxidation is synthesized the results are shown in tables 1.
Table 1
Claims (10)
1. a kind of hydrogen peroxide synthesis loaded catalyst, which is characterized in that catalyst activity component is Metal Palladium, and catalyst carries
Body is acid carrier；The loading of palladium is 0.1%-20%, is preferably 1%-5%.
2. loaded catalyst according to claim 1, which is characterized in that catalyst carrier include oxide, molecular sieve,
Carbon material；Catalyst activity component is made of palladium, and the loading of palladium is 0.1%-10%, and the grain size of palladium is 0.5nm-15nm.
3. loaded catalyst according to claim 2, which is characterized in that oxide is selected from oxidation in catalyst carrier
It is more than one or both of silicon, aluminium oxide, titanium oxide, zirconium oxide, cerium oxide or lanthana；Molecular sieve includes ZSM-5, TS-
1st, more than one or both of 5A, 4A or 13X；Carbon material is included in carbon nanotubes, Nano carbon balls, carbon fiber or graphene
It is one or more kinds of.
4. a kind of preparation method of any loaded catalysts of claim 1-3, which is characterized in that prepared by colloid method
Load type palladium catalyst.
5. preparation method according to claim 4, which is characterized in that polyvinylpyrrolidone PVP and palladium salt difference is molten
In Xie Yushui, then by above two solution be mixed 0.5-8 it is small when, weigh reducing agent, be dissolved in ice water, by dissolving also
Former agent solution disposably pour into polyvinylpyrrolidone PVP protection palladium colloidal sol in, continue stir 0.5-5 it is small when, obtain colloidal sol,
Catalyst carrier is weighed, is added in colloidal sol, the pH of colloidal sol is adjusted by dust technology, the pH value of solution is made to reach the grade electricity of carrier
Point, continue to stir 0.5-6 it is small when after, dry with deionized water by catalyst detergent to neutrality, roasting obtains the support type
Catalyst.
6. preparation method according to claim 5, which is characterized in that the molar ratio of polyvinylpyrrolidone PVP and palladium salt
For 0.5:1~50:1；The ratio of reducing agent and palladium salt is 0.5:1~5:1；Catalyst drying temperature is 60-150 DEG C, when dry
Between for 10-24 it is small when；Calcination temperature is 300-800 DEG C, when roasting time is 1-6 small.
7. preparation method according to claim 5, which is characterized in that polyvinylpyrrolidone concentration soluble in water is 5-
20000ppm, palladium salt concentration soluble in water are 10-20000ppm；Dust technology molar concentration is 0.01~2mol/L.
8. preparation method according to claim 5, which is characterized in that reducing agent includes sodium borohydride, citric acid, Vitamin C
Acid；
The molecular weight of polyvinylpyrrolidone PVP is 5000-100000, and preferred molecular weight is 10000-30000；
Palladium salt includes nitrate, chlorate, acetate, the preferred palladium nitrate of palladium salt, palladium, palladium acetylacetonate, palladium bichloride.
9. loaded catalyst described in a kind of claim 1 directly synthesizes the application in hydrogen peroxide reaction in hydrogen-oxygen, feature exists
In methanol with aqueous sulfuric acid is mixed, NaBr and catalyst are added in, in the hydrogen of certain pressure, oxygen and argon gas gaseous mixture
It is reacted under atmosphere.
10. application according to claim 9, which is characterized in that
The mass ratio of the reaction system each component is：
The volume ratio of methanol and aqueous sulfuric acid is 4:1~1:4, the concentration of sodium bromide is 0.001~1mol/L, the sulfuric acid water
Solution concentration is 0.2~4mol/L, and gas pressure is 0.5~10Mpa, and gas ratio of components is H2/O2/N2=1~5%:2~
20%:75~97%, the temperature of reaction is -5~40 DEG C, when the time of reaction is 10 minutes~10 small.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999902A (en) * | 2019-04-11 | 2019-07-12 | 浙江工业大学 | The supported porous grade titanium-silicon molecular sieve catalyst of encapsulation type platinum family sub-nanometer metal and its preparation and application |
| CN111250118A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Palladium-based catalyst and application thereof in synthesis of hexamethylene diamine |
| CN111871411A (en) * | 2020-07-27 | 2020-11-03 | 南京工业大学张家港产业学院 | Composite titanium oxide supported noble metal catalyst for hydrogen peroxide synthesis, and preparation method and application method thereof |
| CN112387273A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded carbon fiber catalyst material |
| CN112654425A (en) * | 2018-09-13 | 2021-04-13 | 三菱瓦斯化学株式会社 | Palladium-containing composition and method for producing hydrogen peroxide |
| CN112718012A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method thereof |
| CN113385218A (en) * | 2021-07-15 | 2021-09-14 | 中科三清科技有限公司 | Denitration catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN101850265A (en) * | 2010-06-11 | 2010-10-06 | 中国海洋石油总公司 | Method for preparing catalyst by hydrofining lubricating oil and application of catalyst |
| CN104475092A (en) * | 2014-11-17 | 2015-04-01 | 贵州大学 | Supported Pd catalyst for directly synthesizing hydrogen peroxide and preparation method thereof |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
-
2016
- 2016-11-10 CN CN201610988433.1A patent/CN108067220A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN101850265A (en) * | 2010-06-11 | 2010-10-06 | 中国海洋石油总公司 | Method for preparing catalyst by hydrofining lubricating oil and application of catalyst |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN104475092A (en) * | 2014-11-17 | 2015-04-01 | 贵州大学 | Supported Pd catalyst for directly synthesizing hydrogen peroxide and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SEONGMIN KIM等: "Direct synthesis of hydrogen peroxide from hydrogen and oxygen over single-crystal cubic palladium on silica catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| SEONGMIN KIM等: "Effect of Pd Particle Size on the Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over Pd Core–Porous SiO2 Shell Catalysts", 《CATAL LETT》 * |
| 刘时杰编: "《铂族金属冶金学》", 30 June 2013, 中南大学出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112654425A (en) * | 2018-09-13 | 2021-04-13 | 三菱瓦斯化学株式会社 | Palladium-containing composition and method for producing hydrogen peroxide |
| CN111250118A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Palladium-based catalyst and application thereof in synthesis of hexamethylene diamine |
| CN111250118B (en) * | 2018-11-30 | 2021-06-01 | 中国科学院大连化学物理研究所 | Palladium-based catalyst and application thereof in synthesis of hexamethylene diamine |
| CN109999902A (en) * | 2019-04-11 | 2019-07-12 | 浙江工业大学 | The supported porous grade titanium-silicon molecular sieve catalyst of encapsulation type platinum family sub-nanometer metal and its preparation and application |
| CN112718012A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method thereof |
| CN112718012B (en) * | 2019-10-28 | 2023-10-10 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method thereof |
| CN111871411A (en) * | 2020-07-27 | 2020-11-03 | 南京工业大学张家港产业学院 | Composite titanium oxide supported noble metal catalyst for hydrogen peroxide synthesis, and preparation method and application method thereof |
| CN112387273A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded carbon fiber catalyst material |
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