CN104084195B - A kind of support type spheric active Pd/carbon catalyst and preparation method thereof - Google Patents
A kind of support type spheric active Pd/carbon catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104084195B CN104084195B CN201410330291.0A CN201410330291A CN104084195B CN 104084195 B CN104084195 B CN 104084195B CN 201410330291 A CN201410330291 A CN 201410330291A CN 104084195 B CN104084195 B CN 104084195B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- support type
- preparation
- carbon
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of support type spheric active Pd/carbon catalyst and preparation method thereof, belong to chemical catalyst technical field.This catalyst is carried on average diameter 0.6～1.5mm, specific surface area >=600m by Pt or Pd or two kinds2/ g, the ball shape active carbon carrier surface of dust rate ＜ 0.5% is constituted.By Colophonium and naphthalene Hybrid Heating are modulated, then prepare bitumen ball by suspension method, then carry out successively aoxidizing non-fusible, carbonization and activation processing, prepare asphalt-base spherical activated carbon, successively with pickling be washed to neutrality, obtain catalyst carrier；Described carrier impregnation is loaded in the alcohol solution containing metal precursor, reduces with hydrogen or reducing solution after drying, obtain described catalyst.Described catalyst carrier specific surface area is high, and the rate of metal loaded is high, and catalyst surface is smooth, profile is homogeneous, resistance is little, mechanical strength is high, dust rate is low, the life-span is long, and at room temperature catalysis activity and the stability of PARA FORMALDEHYDE PRILLS(91,95) are higher.
Description
Technical field
The present invention relates to a kind of support type spheric active Pd/carbon catalyst and preparation method thereof, use particularly to one
Support type spheric active Pd/carbon catalyst in room temperature purifying formaldehyde and preparation method thereof, belongs to chemical catalyst skill
Art field.
Background technology
Formaldehyde, also known as formaldehyde, is one of topmost pollutant in indoor environment, has extremely strong carcinogenesis.
Research shows that formaldehyde is the material that a kind of toxicity is higher, and short term contact can stimulate eyes, nasal cavity and respiratory tract,
Long Term Contact low dosage formaldehyde can increase suffers from nasopharyngeal carcinoma and leukemic probability.China's national Specification
The concentration limit of formaldehyde in indoor air pollutant be 0.08mg/m3.At present, formaldehyde in China's indoor environment
The situation of concentration over-standard is very serious, finds according to the sampling Detection investigation of Center for Disease Control (CDC) of country, China
There is concentration of formaldehyde excessive problem in the new finishing residential building of more than 60%, healthy to people causes pole
Big harm.Therefore, study formaldehyde in air purification techniques, improve IAQ (indoor air quality), have the heaviest
The meaning wanted.
The method of purifying formaldehyde includes absorption method, chemical reaction method and catalytic oxidation.Absorption method is commonly used
Adsorbent is porous material such as activated carbon, the molecular sieve etc. of high-ratio surface.But formaldehyde molecule has stronger pole
Property, the absorption on the materials such as nonpolar or low pole activated carbon of the room-temperature gaseous formaldehyde is the most weak, in reality
Border application typically requires and porous mass is modified, to improve its absorbability.But, no matter physics
Absorption or chemisorbed all can not obtain satisfied effect, because after absorption is saturated, adsorbent will lose
Effect.Chemical reaction method is reacted with formaldehyde by chemical reagent and reaches to remove the formaldehyde in air.Common chemistry
Reaction method be by the potassium permanganate being supported on aluminium oxide or activated carbon by oxidation of formaldehyde generate carbon dioxide and
Water, but potassium permanganate load capacity is limited, and after consuming completely, just PARA FORMALDEHYDE PRILLS(91,95) loses detergent power.Organic amine passes through
With formaldehyde complexation generate other chemical substance also can purifying formaldehyde in short-term, but typically cost is higher and is generated
Material itself has certain toxicity.Therefore chemical reaction method is a kind of effective method of short-term, thereby increases and it is possible to make
Become secondary pollution.
Catalytic oxidation purifying formaldehyde is a kind of long-acting method, and oxidation catalyst can be at a lower temperature
Oxygen in catalytic air and formaldehyde react generation carbon dioxide and water, are inherently eliminated formaldehyde.In recent years,
Catalytic oxidation technologies achieves bigger progress and breakthrough in terms of purifying indoor formaldehyde research.
CN10127428A discloses a kind of efficient oxidation at room temperature oxidized the formaldehyde into as carbon dioxide and water and is catalyzed
Agent, this catalyst with scribble Co-Ce-Sn porous composite oxide cordierite honeycomb ceramic as carrier, with
The Pt of 0%～10% is active component, and with MoO3、CuOx、MnOx、TiO2Deng as auxiliary agent.
CN102247842A discloses a kind of the urging of low concentration formaldehyde in purifying the air of a room under the conditions of ambient temperature and moisture
Agent, this catalyst is to scribble TiO2-SnO2The cordierite honeycomb ceramic of composite oxides is carrier, with 0%～
The Pt of 5% is active component.Conjugation between above-mentioned catalyst monolith pottery and composite oxides is more weak, easily
, during long-term use, there is catalytic mechanical intensity low in dry linting, dry linting phenomenon is serious, catalyst
The problems such as activity is unstable.
CN102836735A discloses one and has the molecular sieve carried type of micropore-mesopore manganese concurrently efficiently except formaldehyde is catalyzed
Agent, it is characterised in that use and scribble that to have the ceramic honey comb of micropore-mesopore manganese molecular sieve concurrently be carrier, with 0%～5%
Pt be active component.This catalyst manganese preparation of molecular sieve is complicated, and poor with the conjugation of ceramic honey comb,
Easy dry linting under high-speed.
CN102941111A discloses the catalyst of a kind of metal carrier load for room temperature purifying formaldehyde, should
Catalyst is made up of FeCrAl alloy, porous inorganic oxide and noble metal active component and auxiliary agent, your gold
Belonging to active component content is 0.1%～10%.Between this catalyst metal carrier and porous oxide, adhesion is weak,
Carrier specific surface area is less, and active component is easy to fall off.
CN103736484A discloses a kind of support type integral catalyzer for purifying formaldehyde, this catalyst
Being with titania nanotube as carrier, load 0.05%～10% noble metal is active component.This catalyst becomes
This is higher, and catalyst performance is unstable, is susceptible to deactivation phenomenom.
The commonly used binary vector of catalyst of the prior art, will porous oxide be coated in cordierite or
Make carrier on alloy, there is the shortcomings such as adhesion between carrier binary composition is weak, carrier specific surface area is little, from
And cause that catalyst strength dry linting low, easy, noble metal utilization efficiency be low, high in cost of production shortcoming.
Summary of the invention
The defect existed for prior art, an object of the present invention is to provide a kind of spherical work of support type
Property Pd/carbon catalyst, described catalyst with the ball shape active carbon of high-specific surface area as carrier, smooth surface, profile
Homogeneous, resistance is little, mechanical strength is high and dust rate is low, described catalyst noble metal utilization rate is high, and the life-span is long,
Can at room temperature keep catalysis activity and stability that PARA FORMALDEHYDE PRILLS(91,95) is higher, can be widely applied to the first of various environment
The removal of aldehyde pollutant.
The two of the purpose of the present invention are to provide the preparation method of a kind of support type spheric active Pd/carbon catalyst.
In order to reach described purpose, the present invention adopts the following technical scheme that
A kind of support type spheric active Pd/carbon catalyst, described catalyst by metal load in spheric active high-area carbon
Surface is constituted, and described metal is platinum (Pt) or palladium (Pd) or two kinds；Described spheric active high-area carbon is average
A diameter of 0.6mm～1.5mm, specific surface area >=600m2/ g, dust rate ＜ 0.5%.
Being in terms of 100% by the oeverall quality of described catalyst, the quality of the most described metal is 0.05%～1%.
The preparation method of a kind of support type spheric active Pd/carbon catalyst of the present invention, described method step is as follows:
(1) preparation of carrier
Add in reactor after Colophonium is mixed with naphthalene, be heated to 180 DEG C～250 DEG C of stirring >=3h, be cooled to
≤ 100 DEG C of taking-ups cooling obtain block mixture；Block mixture is crushed to particle diameter be 0.6mm～
The modulation Colophonium of 1.5mm, with polyvinyl alcohol water solution as dispersant, uses suspension method to prepare bitumen ball；
Bitumen ball is warming up to 280 DEG C～300 DEG C with the heating rate of≤0.2 DEG C/min in atmosphere and keeps >=6h
Carry out aoxidizing cure treatment；Bitumen ball after peroxidating cure treatment is protected at nitrogen or noble gas
Protecting down and be warming up to 600 DEG C～800 DEG C of carbonization 1h～3h with the heating rate of≤5 DEG C/min, carbonization terminates follow-up
Continuous being warming up to 800 DEG C～900 DEG C and be passed through steam and carry out activation processing, soak time is 0.5h～2h,
To asphalt-base spherical activated carbon；After the pickling of asphalt-base spherical activated carbon elder generation, it is washed to neutrality, obtains spherical work
Property high-area carbon；
Wherein, the softening point of described Colophonium is 150 DEG C～280 DEG C, preferably 200 DEG C～280 DEG C；
Described naphthalene is 1:1～1:4 with the mass ratio of Colophonium；
Preferred mass percent be the polyvinyl alcohol water solution of 2% be dispersant；
The preferred preparation condition of suspension method is: stirring at 100 DEG C～110 DEG C, mixing speed is 300rpm；
Preferably bitumen ball is warming up to 300 DEG C with the heating rate of≤0.2 DEG C/min in atmosphere；Preferably keep
6h～12h carries out aoxidizing cure treatment；
Preferably by the bitumen ball after peroxidating cure treatment under nitrogen or inert gas shielding with 5 DEG C
The heating rate of/min heats up；
Acid used by described pickling is preferably nitric acid；It is more preferably the nitric acid that mass percent is 2%～4% molten
Liquid.
(2) load of active component
Ball shape active carbon carrier impregnation is loaded in the alcohol solution containing metal precursor, described
The mass ratio of carrier and alcohol solution is 1:2～1:5, and dip time is 2h～40h, then at 60 DEG C～
150 DEG C of drying, then reduce with hydrogen or reducing solution, obtain a kind of support type of the present invention spherical
Activated-carbon catalyst；
Described metal precursor is that Palladous chloride., Palladous nitrate., platinum chloride, chloroplatinic acid or chlorine palladium are sour or two or more；
Described alcohol solution is ethanol, propanol or butanol aqueous solution, and wherein, the mass percent of alcohol is
20%～80%；Being preferably ethanol water, wherein, the mass percent of ethanol is 20%～80%；
When using hydrogen reducing, reduction temperature is 300 DEG C～600 DEG C, recovery time >=2h；
When reducing with reducing solution, the reducing agent in described reducing solution is formaldehyde, formic acid or hydroboration
Sodium, described reducing agent is 10:1～100:1 with the mol ratio of metal, needs to be dried after reduction.
Beneficial effect
1. the invention provides a kind of support type spheric active Pd/carbon catalyst and preparation method thereof, described catalyst
Carrier there is high specific surface area, the utilization rate of metal active constituent can be greatly improved, reduce metal and contain
Amount；
2. the invention provides a kind of support type spheric active Pd/carbon catalyst and preparation method thereof, described catalyst
Smooth surface, profile are homogeneous, resistance is little, mechanical strength is high and dust rate is low；
3. the invention provides a kind of support type spheric active Pd/carbon catalyst and preparation method thereof, described catalyst
At room temperature PARA FORMALDEHYDE PRILLS(91,95) has higher catalysis activity and stability, and service life is long.
Accompanying drawing explanation
Fig. 1 is the microphotograph of the spheric active high-area carbon of embodiment 1.
Fig. 2 is the microphotograph of the spheric active high-area carbon of embodiment 2～6.
Fig. 3 is the microphotograph of the spheric active high-area carbon of embodiment 7～9.
Detailed description of the invention
Following instance only further illustrates the present invention, is not limiting as the scope of protection of the invention.
Embodiment 1
(1) joining volume with 500g naphthalene after being mixed by the Colophonium that 1000g softening point is 230 DEG C is 2L's
In autoclave, it is heated to 200 DEG C of stirring 3h, is cooled to 100 DEG C of taking-ups and cooling obtains block mixture,
Block mixture crushing and screening is obtained the modulation Colophonium that particle diameter is 0.6mm～1.5mm；With the poly-second of 2wt%de
Enol aqueous solution is dispersant, and at 110 DEG C, mixing speed is to prepare in a kettle. under conditions of 300rpm
Obtain bitumen ball；Bitumen ball is warming up to 300 DEG C with the heating rate of 0.2 DEG C/min in atmosphere and keeps 6h
Carry out aoxidizing cure treatment；By the bitumen ball after peroxidating cure treatment under nitrogen protection with 5 DEG C
After the heating rate of/min is warming up to 600 DEG C of carbonization 2h, it is warming up to 800 DEG C and is passed through steam and activates
Processing, soak time is 1.5h, i.e. obtains asphalt-base spherical activated carbon；The asphalt-base spherical activity that will obtain
The HNO of charcoal 2wt%3Aqueous solution soaks 1h at 80 DEG C, is washed with deionized water after being 6～7 to pH value
It is dried, i.e. obtains spheric active high-area carbon.
(2) by spheric active high-area carbon containing PtCl2Ethanol water in impregnate 4h, ethanol water
The mass percent of middle ethanol is 50%, and described carrier is 1:2 with the mass ratio of ethanol water, with described
Catalyst oeverall quality meter, the mass percent of Pt is 0.1%, by the catalyst carrier after dipping at 110 DEG C
Drying, 400 DEG C of reduction 3h in hydrogen, obtain a kind of support type spheric active Pd/carbon catalyst afterwards.
Embodiment 2
(1) joining volume with 500g naphthalene after being mixed by the Colophonium that 1000g softening point is 280 DEG C is 2L's
In autoclave, it is heated to 250 DEG C of stirring 3h, is cooled to 100 DEG C of taking-ups and cooling obtains block mixture,
Block mixture crushing and screening is obtained the modulation Colophonium that particle diameter is 0.6mm～1.5mm；Polyethylene with 2wt%
Alcohol-water solution is dispersant, and at 110 DEG C, mixing speed is to be prepared in a kettle. under conditions of 300rpm
To bitumen ball；Bitumen ball is warming up to 300 DEG C with the heating rate of 0.2 DEG C/min in atmosphere and keeps 6h
Carry out aoxidizing cure treatment；By the bitumen ball after peroxidating cure treatment under nitrogen protection with 5 DEG C
After the heating rate of/min is warming up to 600 DEG C of carbonization 2h, it is warming up to 800 DEG C and is passed through steam and activates
Processing, soak time is 1.5h, i.e. obtains asphalt-base spherical activated carbon；The asphalt-base spherical activity that will obtain
The HNO of charcoal 2wt%3Aqueous solution soaks 1h at 80 DEG C, is washed with deionized water after being 6～7 to pH value
It is dried, i.e. obtains spheric active high-area carbon.
(2) by spheric active high-area carbon containing PtCl2Ethanol water dipping 4h, in ethanol water
The mass percent of ethanol is 50%, and described carrier is 1:2 with the mass ratio of ethanol water, urges with described
Agent oeverall quality meter, Pt mass percent is 0.1%, by the catalyst carrier after dipping 110 DEG C of drying,
400 DEG C of reduction 3h in hydrogen, obtain a kind of support type spheric active Pd/carbon catalyst afterwards.
Embodiment 3
Spheric active high-area carbon embodiment 2 step (1) prepared is containing PtCl2Ethanol water in
Dipping 4h, in ethanol water, the mass percent of ethanol is 50%, described carrier and the matter of ethanol water
Amount ratio is 1:2, and in terms of described catalyst oeverall quality, Pt mass percent is 0.3%, urging after impregnating
Agent carrier is 110 DEG C of drying, and 400 DEG C of reduction 3h in hydrogen, obtain a kind of support type spheric active afterwards
Pd/carbon catalyst.
Embodiment 4
Spheric active high-area carbon embodiment 2 step (1) prepared is containing PtCl2Ethanol water in
Dipping 4h, in ethanol water, the mass percent of ethanol is 50%, described carrier and the matter of ethanol water
Amount ratio is 1:2, and in terms of described catalyst oeverall quality, Pt mass percent is 0.5%, urging after impregnating
Agent carrier is 110 DEG C of drying, and 400 DEG C of reduction 3h in hydrogen, obtain a kind of support type spheric active afterwards
Pd/carbon catalyst.
Embodiment 5
Spheric active high-area carbon embodiment 2 step (1) prepared is containing PtCl2Ethanol water in
Dipping 4h, in ethanol water, the mass percent of ethanol is 50%, described carrier and the matter of ethanol water
Amount ratio is 1:2, and in terms of described catalyst oeverall quality, Pt mass percent is 0.8%, urging after impregnating
Agent carrier is 110 DEG C of drying, and 400 DEG C of reduction 3h in hydrogen, obtain a kind of support type spheric active afterwards
Pd/carbon catalyst.
Embodiment 6
Spheric active high-area carbon embodiment 2 step (1) prepared is containing PtCl2Ethanol water in
Dipping 4h, in ethanol water, the mass percent of ethanol is 50%, described carrier and the matter of ethanol water
Amount ratio is 1:2, and in terms of described catalyst oeverall quality, Pt mass percent is 0.5%, urging after impregnating
Agent carrier, 110 DEG C of drying, reduces afterwards in sodium borohydride aqueous solution, sodium borohydride and Pt mole
Ratio is 20:1, obtains a kind of support type spheric active Pd/carbon catalyst after drying.
Embodiment 7
(1) height that volume is 2L is joined with 500g naphthalene after being mixed by the Colophonium that 750g softening point is 280 DEG C
In pressure reactor, it is heated to 250 DEG C of stirring 3h, is cooled to 100 DEG C of taking-ups and cooling obtains block mixture,
Block mixture crushing and screening is obtained the modulation Colophonium that particle diameter is 0.6mm～1.5mm；Polyethylene with 2wt%
Alcohol-water solution is dispersant, and at 100 DEG C, mixing speed is to be prepared in a kettle. under conditions of 300rpm
To bitumen ball；Bitumen ball is warming up to 300 DEG C with the heating rate of 0.2 DEG C/min in atmosphere and keeps 12h
Carry out aoxidizing cure treatment；By the bitumen ball after peroxidating cure treatment under nitrogen protection with 5 DEG C
After the heating rate of/min is warming up to 600 DEG C of carbonization 2h, it is warming up to 900 DEG C and is passed through steam and activates
Processing, soak time is 1h, i.e. obtains asphalt-base spherical activated carbon；The asphalt-base spherical activated carbon that will obtain
With the HNO of 2wt%3Aqueous solution soaks 1h at 80 DEG C, be washed with deionized water to pH value be after 6～7 dry
Dry, i.e. obtain spheric active high-area carbon.
(2) by spheric active high-area carbon containing PtCl2With Pd (NO3)2Ethanol water in impregnate 4h,
In ethanol water, the mass percent of ethanol is 50%, and described carrier is 1 with the mass ratio of ethanol water:
4, in terms of described catalyst oeverall quality, the mass percent of Pt and Pd is followed successively by 0.3% and 0.2% respectively,
By the catalyst carrier after dipping 110 DEG C of drying, 500 DEG C of reduction 3h in hydrogen afterwards, obtain a kind of negative
Load type spheric active Pd/carbon catalyst.
Embodiment 8
Spheric active high-area carbon embodiment 7 step (1) prepared is containing PtCl2With Pd (NO3)2Second
Impregnating 24h in alcohol-water solution, in ethanol water, the mass percent of ethanol is 25%, described carrier and ethanol
The mass ratio of aqueous solution is 1:4, and in terms of described catalyst oeverall quality, the mass percent of Pt and Pd is respectively
It is followed successively by 0.1% and 0.4%, by the catalyst carrier after dipping 110 DEG C of drying, in hydrogen 500 DEG C afterwards
Reduction 3h, obtains a kind of support type spheric active Pd/carbon catalyst.
Embodiment 9
Spheric active high-area carbon embodiment 7 step (1) prepared is containing Pd (NO3)2Ethanol water
Middle dipping 4h, in ethanol water, the mass percent of ethanol is 50%, described carrier and ethanol water
Mass ratio is 1:2, and in terms of described catalyst oeverall quality, the mass percent of Pd is 0.5%, after impregnating
Catalyst carrier 110 DEG C of drying, 500 DEG C of reduction 3h in hydrogen, obtain a kind of support type spherical afterwards
Activated-carbon catalyst.
Respectively the support type spheric active Pd/carbon catalyst of embodiment 1～9 preparation is tested, specific as follows:
(1) carrying out purifying formaldehyde performance test in fixed bed reactors, experiment condition is as follows: described catalysis
Agent consumption is 10g, and in reaction system, the percentage by volume of oxygen is 20%, and the percentage by volume of nitrogen is
80%, formaldehyde gas is produced by formalin bubbling, nitrogen bring reaction system into, controls import concentration of formaldehyde
For 5mg/m3, reaction velocity is 50000h-1, reaction temperature is room temperature；
(2) specific surface area of described catalyst uses U.S.'s health tower Autosorb-1 physical adsorption appearance to utilize BET
Method records；
(3) described catalyst dust rate test: under room temperature condition, in deionized water, by described catalyst
Before and after 40kHz sonic oscillation 10min, test vibration, the weight difference of catalyst obtains dust rate；
(4) utilize Nikon company Eclipse E100 type microscope to the ball shape active carbon of preparation in embodiment
Carrier is observed, and passes through microscopic image analysis system acquisition and calculate sphericity, to obtain described load
The shape informations such as the sphericity of body and smooth surface degree；Sphericity is semi-minor axis and the major semiaxis of described carrier
Ratio, average spherical degree is the meansigma methods of the sphericity no less than 30 described carriers.
Every test the results are shown in Table 1.
Table 1
Claims (8)
1. the preparation method of a support type spheric active Pd/carbon catalyst, it is characterised in that: described catalyst by
Metal load is constituted in ball shape active carbon carrier surface, and metal is Pt and/or Pd；Described ball shape active carbon carries
Body average diameter is 0.6mm～1.5mm, specific surface area >=600m2/ g, dust rate ＜ 0.5%；Urge with described
The oeverall quality of agent is 100% meter, and the quality of metal is 0.05%～1%；
Step is as follows:
(1) preparation of carrier
Add in reactor after Colophonium is mixed with naphthalene, be heated to 180 DEG C～250 DEG C of stirring >=3h, be cooled to
≤ 100 DEG C of taking-ups cooling obtain block mixture；Block mixture is crushed to particle diameter be 0.6mm～
The modulation Colophonium of 1.5mm, with polyvinyl alcohol water solution as dispersant, uses suspension method to prepare bitumen ball；
Bitumen ball is warming up to 280 DEG C～300 DEG C with the heating rate of≤0.2 DEG C/min in atmosphere and keeps >=6h
Carry out aoxidizing cure treatment；Bitumen ball after peroxidating cure treatment is protected at nitrogen or noble gas
Protecting down and be warming up to 600 DEG C～800 DEG C of carbonization 1h～3h with the heating rate of≤5 DEG C/min, carbonization terminates follow-up
Continuous being warming up to 800 DEG C～900 DEG C and be passed through steam and carry out activation processing, soak time is 0.5h～2h,
To asphalt-base spherical activated carbon；By asphalt-base spherical activated carbon first with washing with water after pickling to neutrality, obtain ball
Shape absorbent charcoal carrier；
Wherein, the softening point of Colophonium is 150 DEG C～280 DEG C；
Naphthalene is 1:1～1:4 with the mass ratio of Colophonium；
(2) load of active component
Ball shape active carbon carrier impregnation is loaded in the alcohol solution containing metal precursor, described
The mass ratio of carrier and alcohol solution is 1:2～1:5, and dip time is 2h～40h, then at 60 DEG C～
150 DEG C of drying, then reduce with hydrogen or reducing solution, obtain a kind of support type spheric active Pd/carbon catalyst；
Wherein, metal precursor be Palladous chloride., Palladous nitrate., platinum chloride, chloroplatinic acid or chlorine palladium acid or two kinds with
On mixing；
Alcohol solution is ethanol, propanol or butanol aqueous solution, and the mass percent of alcohol is 20%～80%；
When using hydrogen reducing, reduction temperature is 300 DEG C～600 DEG C, recovery time >=2h；
When reducing with reducing solution, the reducing agent in reducing solution is formaldehyde, formic acid or sodium borohydride,
Reducing agent is 10:1～100:1 with the mol ratio of metal, needs to be dried after reduction.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: the softening point of Colophonium described in step (1) is 200 DEG C～280 DEG C.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: described in step (1), in polyvinyl alcohol water solution, the mass percent of polyvinyl alcohol is 2%.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: suspension method described in step (1) is particularly as follows: stir at 100 DEG C～110 DEG C, and mixing speed is
300rpm。
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: bitumen ball is warming up to 300 DEG C with the heating rate of≤0.2 DEG C/min in (1) by step in atmosphere,
6h～12h is kept to carry out aoxidizing cure treatment.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: by the bitumen ball after peroxidating cure treatment in nitrogen or inert gas shielding in step (1)
Under heat up with the heating rate of 5 DEG C/min.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: acid used by pickling described in step (1) be mass percent be the salpeter solution of 2%～4%.
The preparation method of a kind of support type spheric active Pd/carbon catalyst the most according to claim 1, it is special
Levy and be: described in step (2), alcohol solution is ethanol water, the mass percent of ethanol be 20%～
80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410330291.0A CN104084195B (en) | 2014-07-11 | 2014-07-11 | A kind of support type spheric active Pd/carbon catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410330291.0A CN104084195B (en) | 2014-07-11 | 2014-07-11 | A kind of support type spheric active Pd/carbon catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104084195A CN104084195A (en) | 2014-10-08 |
| CN104084195B true CN104084195B (en) | 2016-08-17 |
Family
ID=51632012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410330291.0A Active CN104084195B (en) | 2014-07-11 | 2014-07-11 | A kind of support type spheric active Pd/carbon catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104084195B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318425B (en) * | 2016-08-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | One kind micro mist containing naphthalene pitch prepares grade bitumen ball method |
| CN106744933B (en) * | 2016-11-16 | 2019-03-05 | 俞祥敏 | A kind of preparation method being suitble to industrial asphalt-base spherical activated carbon |
| CN108236950A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the Pd-B/C powder as formaldehyde remover |
| CN108236951A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the palladium on carbon powder as formaldehyde remover |
| CN108236952A (en) * | 2016-12-27 | 2018-07-03 | 天津众华鑫环保科技有限公司 | A kind of preparation method of noble metal formaldehyde remover radiator coating |
| CN108610792A (en) * | 2016-12-27 | 2018-10-02 | 天津众华鑫环保科技有限公司 | A kind of radiator formaldehyde eliminates the preparation method of coating |
| CN108927146B (en) * | 2017-05-23 | 2021-08-31 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrogenation catalyst and preparation method thereof |
| CN107754792A (en) * | 2017-10-30 | 2018-03-06 | 上海泰坦科技股份有限公司 | A kind of preparation method of spherical mesoporous charcoal supported precious metal catalyst |
| CN107694564B (en) * | 2017-11-23 | 2023-10-03 | 苏州吉派供应链管理有限公司 | Catalyst for decomposing formaldehyde and preparation method thereof |
| CN108554399B (en) * | 2018-05-11 | 2021-02-02 | 武汉轻工大学 | Preparation method of cellulose-based Pd/C catalyst |
| CN108996503B (en) * | 2018-07-16 | 2020-11-03 | 深圳市环球绿地新材料有限公司 | Activation method of spherical activated carbon, product and application thereof |
| CN108946721B (en) * | 2018-07-16 | 2020-10-30 | 深圳市环球绿地新材料有限公司 | Spherical activated carbon with high compressive strength and preparation method and application thereof |
| CN109110758B (en) * | 2018-08-16 | 2020-05-08 | 中钢集团鞍山热能研究院有限公司 | Preparation method of porous carbon electrode material for supercapacitor |
| CN109231200B (en) * | 2018-09-25 | 2019-12-17 | 湖南曦威新材料有限公司 | Preparation method of rock asphalt base spherical activated carbon |
| CN110961096B (en) * | 2018-09-30 | 2022-09-27 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN110354893B (en) * | 2019-07-19 | 2022-04-08 | 三峡大学 | CuOXPreparation method of/OMS-2 catalyst and application of catalyst in degradation of organic pollutants |
| CN111013574A (en) * | 2019-11-13 | 2020-04-17 | 北京博雅合众环保科技有限公司 | Preparation method of noble metal/carbon sphere composite catalytic material for removing formaldehyde from air |
| CN111068666A (en) * | 2019-11-18 | 2020-04-28 | 天津博雅大地新材料科技有限公司 | Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN114797846A (en) * | 2022-05-24 | 2022-07-29 | 四川轻化工大学 | Catalyst for hydrodechlorination and preparation method thereof |
| CN115532254B (en) * | 2022-11-29 | 2023-03-03 | 山东国邦药业有限公司 | Preparation method of palladium-carbon catalyst for doxycycline production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057278C (en) * | 1997-01-17 | 2000-10-11 | 中国科学院山西煤炭化学研究所 | Method for preparing globular active carbon |
| CN103787331A (en) * | 2014-02-28 | 2014-05-14 | 东北林业大学 | Preparation method of pitch-based spherical activated carbon with rich meso pores |
-
2014
- 2014-07-11 CN CN201410330291.0A patent/CN104084195B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104084195A (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104084195B (en) | A kind of support type spheric active Pd/carbon catalyst and preparation method thereof | |
| CN109012164B (en) | Nanofiber membrane material capable of decomposing formaldehyde at normal temperature and preparation method and application thereof | |
| Fang et al. | Efficient MnOx supported on coconut shell activated carbon for catalytic oxidation of indoor formaldehyde at room temperature | |
| CN103736484B (en) | A kind of support type class integral catalyzer for purifying formaldehyde and preparation method thereof | |
| CN104368335B (en) | A kind of preparation method and applications of purifying formaldehyde noble metal monolithic catalyst | |
| CN106140090B (en) | It is a kind of for removing the MnO of indoor formaldehyde2- ACF material and preparation method thereof | |
| CN102247746B (en) | Formaldehyde elimination agent and preparation method thereof | |
| CN106925265B (en) | A kind of transition metal composite oxide catalytic agent | |
| CN102836712A (en) | Catalyst for completely removing formaldehyde in indoor air at room temperature | |
| CN107159202B (en) | Manganese-doped palladium supported catalyst and preparation method and application thereof | |
| CN108816244B (en) | Nano carbon-based composite material for catalytic oxidation degradation of formaldehyde and preparation method and application thereof | |
| CN104741000B (en) | A kind of application of composite bed low temperature SCR denitration catalyst | |
| CN109289837A (en) | A kind of platinum carbon catalyst and its preparation method and application | |
| CN107684916B (en) | Monolithic catalyst using carbonized wood as carrier for removing formaldehyde at low temperature and preparation method thereof | |
| CN102247837B (en) | Titanium oxide supported catalyst for eliminating formaldehyde in microenvironment air | |
| CN103495418A (en) | Macroporous-mesoporous cerium-zirconium solid solution silver-loaded catalyst and preparation method and application thereof | |
| CN107376939A (en) | A kind of preparation method of the activated-carbon catalyst of constant temperature catalyzing decomposing formaldehyde | |
| CN103638981A (en) | Supported type Au catalyst containing organic polymer electronic auxiliary | |
| CN102240549A (en) | Catalysis technique for high-efficiency, moisture-resistance and room-temperature formaldehyde removal | |
| CN107096380A (en) | A kind of method and apparatus of catalytic oxidation treatment formaldehyde in air | |
| CN113976115B (en) | Layered core-shell structured catalyst, preparation method and application of catalyst in low-temperature catalytic oxidation of toluene | |
| Lu et al. | Room temperature removal of NO by activated carbon fibres loaded with urea and La2O3 | |
| CN110075837A (en) | Metal-metatitanic acid composite oxides preparation method and application | |
| CN108786802A (en) | A kind of room temperature purify the air of a room pollutant method for preparing catalyst and its application | |
| CN106140175A (en) | A kind of be catalyzed burning fluorine-containing, the preparation method of chlorine VOCs catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 056027 No. 17, Exhibition Road, Handan, Hebei Patentee after: 718th Research Institute of China Shipbuilding Corp. Address before: 056027 No. 17, Exhibition Road, Handan, Hebei Patentee before: Handan Purifying Equipment Research Institute |