CN106914278A - A kind of method of the monatomic catalyst stability for improving catalysis burning VOCs - Google Patents
A kind of method of the monatomic catalyst stability for improving catalysis burning VOCs Download PDFInfo
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- CN106914278A CN106914278A CN201710215260.4A CN201710215260A CN106914278A CN 106914278 A CN106914278 A CN 106914278A CN 201710215260 A CN201710215260 A CN 201710215260A CN 106914278 A CN106914278 A CN 106914278A
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Abstract
The invention discloses a kind of method of the monatomic catalyst stability for improving catalysis burning VOCs, comprise the following steps：(1) TRIS buffer containing dopamine is prepared；(2) monatomic catalyst poly-dopamine is prepared；(3) monatomic catalyst poly-dopamine is made annealing treatment so that carbon shell parcel form catalyst atom, is obtained monatomic catalyst carbon shell；(4) the monatomic catalyst carbon shell that will be obtained calcines 2 10h in 300 1000 DEG C of air atmospheres, the carbon shell wrapped up on the monatomic catalyst of burning-off, obtains through the amine-modified monatomic catalyst of DOPA.Using this method through the monatomic catalyst of dopamine modified due to enhancing the active force between catalyst activity component and carrier, therefore stronger anti-agglutinatting property and tolerance is shown during catalysis burning VOCs, greatly extends the service life of monatomic catalyst.
Description
Technical field
It is more particularly to a kind of to improve catalysis burning VOCs the present invention relates to a kind of method of monatomic catalyst stability
Monatomic catalyst stability method.
Background technology
In recent years, volatile organic matter (Volatile Organic Compounds, abbreviation VOCs) has become harm
The important air pollutants of human health, define, 50~260 DEG C of boiling point, at room temperature saturated vapour pressure according to the World Health Organization
Organic compound more than 133Pa is VOC.VOCs originates widely, such as petrochemical industry, coating, skin
There are a large amount of VOCs to produce during the industry productions such as leather, electronics, printing, baking vanish, pharmacy, printing, and there is excitant mostly
Smell.It is chronically at very big to human health damage under VOCs contents environment high, there is teratogenesis, carcinogenic, mutagenesis.VOCs bands
The serious harm for coming causes the great attention of State-level, Environmental Protection Department issue in 2010《On propulsion atmosphere pollution connection
Anti- joint control work improves the instruction of region air quality》(Office of the State Council send out [2010] No. 33), indicate China using VOCs as
Priority pollutant, and expand comprehensive prevention and control in key industry and major fields；What on January 1st, 2016 implemented《China
People's republic's Air Pollution Prevention Law》Indicate that China has gone to that there are laws to abide by the stage for comprehensive control atmosphere pollution.
At present, administering the method for VOCs mainly has absorption hair, combustion method (including directly burning and catalysis burning), biological
Method, condensation method, corona method, membrane separation process etc..Wherein, Production by Catalytic Combustion Process because with clearance is high, energy consumption is low, secondary pollution is small,
Applied widely the advantages of, is as the main method for administering VOCs at present.
The key of Production by Catalytic Combustion Process is the selection of catalyst, and the catalyst of function admirable can not only play catalytic degradation
The effect of VOCs, and also there is anti-agglutinatting property and stiff stability to reduce production cost.Publication No.
" a kind of Production by Catalytic Combustion Process removes low concentration volatile organic matter catalyst and preparation side to the patent disclosure of CN104874396A
Method ", the catalyst is with γ-A12O3It is carrier, active component is noble metal, and auxiliary agent is non-noble metal oxide.The preparation is urged
Agent advantage is preparation process is simple, low production cost, in system for catalytic combustion to VOC also have compared with
Good removal ability, but the patent does not probe into the stability of catalyst, i.e., with the extension of operating time, catalyst performance
Whether can decline.
The patent disclosure of Publication No. CN106064087A " a kind of method of VOCs catalyst for catalytic combustion ", with gold
Category-organic framework material is prepared for the metal composite oxide of superior catalytic performance for carrier, when temperature reaches more than 300 DEG C
There can be clearance higher to benzene.But active component load capacity is higher, additionally, also the stability not for catalyst is carried out
Probe into.
Monatomic is the new catalyst of a class, and compared to traditional supported catalysts, monatomic catalyst realizes single
Atom turns into reactivity point position, and the load capacity of catalyst is substantially reduced, and catalytic effect is also significantly improved.China's Dalian compound
Institute professor Zhang Tao realizes the monatomic distribution of Pt catalyst by infusion process, and it was found that monatomic distribution catalyst have compared with
Catalysis activity high.At present, the application of monatomic catalyst is yet there are no in system for catalytic combustion, mainly by monatomic catalysis
The stability of agent and the limitation of anti-agglutinatting property.
The content of the invention
Shortcoming it is an object of the invention to overcome prior art, there is provided a kind of raising catalysis burning the monatomic of VOCs is urged
The method of agent stability, this method modifies monatomic catalyst using dopamine coating, by modified monatomic catalyst
Being applied in catalysis burning VOCs systems can be remarkably reinforced the anti-agglutinatting property and stability of catalyst, extend the use longevity of catalyst
Life.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
A kind of method of the monatomic catalyst stability for improving catalysis burning VOCs, comprises the following steps：
(1) TRIS buffer containing dopamine is prepared, is concretely comprised the following steps：By trishydroxymethylaminomethane
The trishydroxymethylaminomethane cushioning liquid for being configured to that concentration is 1-3wt% is diluted with water, then with hydrochloric acid by cushioning liquid pH
Value regulation adds dopamine to 8.0, is made into the trishydroxymethylaminomethane cushioning liquid containing dopamine, described dopamine
Concentration in the trishydroxymethylaminomethane cushioning liquid containing dopamine is 3-20wt%；
(2) monatomic catalyst-poly-dopamine is prepared, is concretely comprised the following steps：
A monatomic catalyst is added the trishydroxymethylaminomethane cushioning liquid containing dopamine by (), be then sufficiently stirred for
Obtain suspension；Described monatomic catalyst is 1 with the mass ratio of cushioning liquid:1-10, described monatomic catalyst
Load capacity is 0.01-1wt%；
B suspension centrifugation is precipitated thing by (), described sediment washing then is gone into the removal of impurity；
C () will remove contamination precipitation thing and be vacuum dried at 60-150 DEG C, obtain monatomic catalyst-poly-dopamine；
(3) annealing temperature be 400-1200 DEG C, annealing rate be 2-8 DEG C/min, annealing the time for 3-5h bar
Under part, monatomic catalyst-poly-dopamine is made annealing treatment so that carbon shell parcel form catalyst atom, obtained monatomic
Catalyst-carbon shell；
(4) the monatomic catalyst-carbon shell that will be obtained calcines 2-10h in 300-1000 DEG C of air atmosphere, and burning-off list is former
The carbon shell wrapped up in muonic catalysis agent, obtains through the amine-modified monatomic catalyst of DOPA.
Beneficial effects of the present invention：
1. the inventive method preparation condition is relatively mild, and reaction condition is simple, i.e. operable under normal temperature, compared to high temperature hydro-thermal
Facture wraps up dopamine coating, and the present invention has significant advantage.
2. through the monatomic catalyst of dopamine modified due to enhancing the effect between catalyst activity component and carrier
Power, therefore stronger anti-agglutinatting property and tolerance is shown during catalysis burning VOCs, greatly extend monatomic urging
The service life of agent, is conducive to the industrial applications of monatomic catalyst.
Specific embodiment
Below in conjunction with case study on implementation of the present invention, the technical scheme in case study on implementation of the present invention is carried out clearly and completely
Description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this hair
Embodiment in bright, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
A kind of method of monatomic catalyst stability for improving catalysis burning VOCs of the invention, comprises the following steps：
(1) TRIS buffer containing dopamine is prepared, is concretely comprised the following steps：By trishydroxymethylaminomethane
The trishydroxymethylaminomethane cushioning liquid for being configured to that concentration is 1-3wt% is diluted with water, then with hydrochloric acid by cushioning liquid pH
Value regulation adds dopamine to 8.0, is made into the trishydroxymethylaminomethane cushioning liquid containing dopamine, described dopamine
Concentration in the trishydroxymethylaminomethane cushioning liquid containing dopamine is 3-20wt%.
Preferably, concentration of the described dopamine in the trishydroxymethylaminomethane cushioning liquid containing dopamine is 7-
15wt%.Available poly-dopamine molecular weight is relatively mild, while can also reduce the dopamine autohemagglutination time.
(2) monatomic catalyst-poly-dopamine is prepared, is concretely comprised the following steps：
A monatomic catalyst is added the trishydroxymethylaminomethane cushioning liquid containing dopamine by (), be then sufficiently stirred for
Obtain suspension；Described monatomic catalyst is 1 with the mass ratio of cushioning liquid:1-10, described monatomic catalyst
Load capacity is 0.01-1wt% (active component and catalyst gross mass ratio).
Preferred monatomic catalyst is 1 with cushioning liquid mass ratio:4-7, the poly-dopamine coating for so being formed is more
It is fine and close.
The load capacity of preferred monatomic catalyst is 0.01-0.2wt%, such active component and poly-dopamine coating it
Between have enough associative keys, can play a part of fully to fix active component.
The active component of described monatomic catalyst is any one in Pt, Pd, Au, Ag, described monatomic to urge
The carrier of agent is alundum (Al2O3), ferroso-ferric oxide, titanium dioxide, cerium oxide, concave convex rod or metal-organic framework materials
Etc. it is therein any one.
B suspension centrifugation is precipitated thing by (), described sediment washing then is gone into the removal of impurity, specific side
Method can be adopted and is washed with deionized 3 times, then be cleaned with ethanol 3 times；
C () will remove contamination precipitation thing and be vacuum dried at 60-150 DEG C, obtain monatomic catalyst-poly-dopamine
(Single-atom catalyst-polydopamine)；
Preferred vacuum drying temperature is 80-120 DEG C.So can effectively remove moisture and prevent active component from reuniting.
(3) annealing temperature be 400-1200 DEG C, annealing rate be 2-8 DEG C/min, annealing the time for 3-5h bar
Under part, monatomic catalyst-poly-dopamine is made annealing treatment so that carbon shell parcel form catalyst atom, obtained monatomic
Catalyst-carbon shell (Single-atom catalyst-carbon shells)；
Preferably, annealing temperature is 700-900 DEG C, and the carbon shell structure and macroscopic property for obtaining at such a temperature are most steady
It is fixed.
(4) the monatomic catalyst-carbon shell that will be obtained calcines 2-10h in 300-1000 DEG C of air atmosphere, and burning-off list is former
The carbon shell wrapped up in muonic catalysis agent, obtains through the amine-modified monatomic catalyst of DOPA.
Preferably, calcining heat is 500-800 DEG C；Preferably, calcination time is 3-6h.This not only increases activearm
Point and carrier contact action power and also enhance the interaction between electronics.
The inventive method, modified monatomic catalyst is applied to substantially to increase in catalysis combustion degradation VOCs systems
The anti-agglutinatting property and stability of powerful catalyst.
Embodiment 1
(1) TRIS buffer containing dopamine is prepared.Trishydroxymethylaminomethane 1.0g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl ammonia that concentration is 1wt%
Methylmethane cushioning liquid.50mL solution is taken, 5.5g dopamines are added, the trihydroxy methyl containing dopamine that concentration is 10wt% is made into
Aminomethane buffer solution.
(2) monatomic catalyst-poly-dopamine is prepared.The monatomic catalyst Pt of 1g is taken, load capacity is 0.02wt% (living
Property component and catalyst gross mass ratio), catalyst carrier is alundum (Al2O3), and it is 10wt% containing dopamine to add concentration
Trishydroxymethylaminomethane cushioning liquid, catalyst is 1 with the mass ratio of solution:4.Magnetic agitation 24h, then by suspension from
The heart is separated, and is precipitated thing, then described sediment is adopted is washed with deionized 3 times, is then cleaned with ethanol 3 times；To remove
Fall contamination precipitation thing to be vacuum dried at 80 DEG C, obtain monatomic catalyst Pt-poly-dopamine.
(3) annealing temperature be 700 DEG C, annealing rate be 2 DEG C/min, under conditions of the annealing time is 5h, will be single
Catalyst atom Pt- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Pt- carbon shells.
(4) the monatomic catalyst Pt-carbon shell that will be obtained calcines 4h in 700 DEG C of air atmospheres, the carbon shell of burning-off parcel,
Obtain through the amine-modified monatomic catalyst Pt of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 4200mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Pt of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 1 is through the amine-modified monatomic catalyst Pt catalytic performance test of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 21 | 99.5 |
| 20 | 21 | 99.5 |
| 30 | 24 | 99.4 |
| 40 | 26 | 99.4 |
| 50 | 26 | 99.4 |
| 60 | 28 | 99.3 |
Table 2 is without the amine-modified monatomic catalyst Pt catalytic performance test of DOPA
Control after the amine-modified monatomic catalyst Pt continuous processing 60h of DOPA as can be seen that using still having more than
Remarkable activity, catalytic performance does not almost change, and the monatomic catalyst Pt amine-modified for being provided without DOPA, when anti-
It is decreased obviously more than catalytic performance after 20h between seasonable, outlet VOCs concentration substantially rises, it is impossible to reach effective degradation effect.With
Upper result illustrates that the present invention can effectively extend service life of the monatomic catalyst Pt in combustion degradation VOCs systems are catalyzed,
With commercial application potentiality.
Embodiment 2
(1) preparation of the TRIS buffer containing dopamine.Trishydroxymethylaminomethane 2.0g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl ammonia that concentration is 2wt%
Methylmethane cushioning liquid.50mL solution is taken, 4.3g dopamines are added, the trihydroxy methyl containing dopamine that concentration is 8wt% is made into
Aminomethane buffer solution.
(2) monatomic catalyst-poly-dopamine is prepared.The monatomic catalyst Pd of 1g is taken, load capacity is 0.01wt% (living
Property component and catalyst gross mass ratio), catalyst carrier is ferroso-ferric oxide, and it is 8wt% containing dopamine to add concentration
Trishydroxymethylaminomethane cushioning liquid, catalyst is 1 with the mass ratio of solution:5.Magnetic agitation 24h, then by suspension from
The heart is separated, and is precipitated thing, is then adopted described sediment and is washed with deionized 3 times, then is cleaned with ethanol 3 times；To remove
Fall contamination precipitation thing to be vacuum dried at 90 DEG C, obtain monatomic catalyst Pd- poly-dopamines.
(3) annealing temperature be 800 DEG C, annealing rate be 4 DEG C/min, under conditions of the annealing time is 4h, will be single
Catalyst atom Pd- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Pd- carbon shells.
(4) the monatomic catalyst Pd- carbon shell that will be obtained calcines 5h in 600 DEG C of air atmospheres, the carbon shell of burning-off parcel,
Obtain through the amine-modified monatomic catalyst Pd of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 4000mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Pd of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 3 is through the amine-modified monatomic catalyst Pd catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 8 | 99.8 |
| 20 | 8 | 99.8 |
| 30 | 10 | 99.7 |
| 40 | 11 | 99.7 |
| 50 | 15 | 99.6 |
| 60 | 15 | 99.6 |
Table 4 is without the amine-modified monatomic catalyst Pd catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 12 | 99.7 |
| 20 | 28 | 99.3 |
| 30 | 108 | 97.3 |
| 40 | 289 | 92.8 |
| 50 | 433 | 89.2 |
| 60 | 705 | 82.4 |
Control after the amine-modified monatomic catalyst Pd continuous processings 60h of DOPA as can be seen that using still having more than
Remarkable activity, catalytic performance does not almost change, and the monatomic catalyst Pd amine-modified for being provided without DOPA, when anti-
It is decreased obviously more than catalytic performance after 20h between seasonable, outlet VOCs concentration substantially rises, it is impossible to reach effective degradation effect.With
Upper result illustrates that the present invention can effectively extend service lifes of the monatomic catalyst Pd in combustion degradation VOCs systems are catalyzed,
With commercial application potentiality.
Embodiment 3
(1) preparation of the TRIS buffer containing dopamine.Trishydroxymethylaminomethane 2.6g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl that concentration is 2.5wt%
Aminomethane buffer solution.50mL solution is taken, 3.8g dopamines are added, the three hydroxyl first containing dopamine that concentration is 7wt% are made into
Base aminomethane buffer solution.
(2) monatomic catalyst-poly-dopamine, is prepared.The monatomic catalyst Au of 1g is taken, load capacity is 0.1wt% (living
Property component and catalyst gross mass ratio), catalyst carrier is titanium dioxide, and it is containing dopamine the three of 7wt% to add concentration
Hydroxymethyl aminomethane cushioning liquid, catalyst is 1 with the mass ratio of solution:6.Magnetic agitation 24h, then suspension is centrifuged
Separate, be precipitated thing, then sediment is adopted and is washed with deionized 3 times, then cleaned with ethanol 3 times；Impurity will be removed
Sediment is vacuum dried at 100 DEG C, obtains monatomic catalyst Au- poly-dopamines.
(3) annealing temperature be 850 DEG C, annealing rate be 6 DEG C/min, under conditions of the annealing time is 3h, will be single
Catalyst atom Au- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Au- carbon shells.
(4) the monatomic catalyst Au- carbon shell that will be obtained calcines 6h in 500 DEG C of air atmospheres, the carbon shell of burning-off parcel,
Obtain through the amine-modified monatomic catalyst Au of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 5000mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Au of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 5 is through the amine-modified monatomic catalyst Au catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 25 | 99.5 |
| 20 | 25 | 99.5 |
| 30 | 27 | 99.4 |
| 40 | 28 | 99.4 |
| 50 | 33 | 99.3 |
| 60 | 33 | 99.3 |
Table 6 is without the amine-modified monatomic catalyst Au catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 30 | 99.4 |
| 20 | 50 | 99.0 |
| 30 | 154 | 96.9 |
| 40 | 339 | 93.2 |
| 50 | 604 | 87.9 |
| 60 | 865 | 82.7 |
Control after the amine-modified monatomic catalyst Au continuous processings 60h of DOPA as can be seen that using still having more than
What remarkable activity, catalytic performance almost change without, and the monatomic catalyst Au amine-modified for being provided without DOPA, when anti-
It is decreased obviously more than catalytic performance after 20h between seasonable, outlet VOCs concentration substantially rises, it is impossible to reach effective degradation effect.With
Upper result illustrates that the present invention can effectively extend service life of the monatomic catalyst in combustion degradation VOCs systems are catalyzed, tool
There is commercial application potentiality.
Embodiment 4
(1) preparation of the TRIS buffer containing dopamine.Trishydroxymethylaminomethane 3.1g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl ammonia that concentration is 3wt%
Methylmethane cushioning liquid.50mL solution is taken, 8.8g dopamines are added, the trihydroxy methyl containing dopamine that concentration is 15wt% is made into
Aminomethane buffer solution.
(2) monatomic catalyst-poly-dopamine is prepared.The monatomic catalyst Ag of 1g is taken, load capacity is 0.2wt% (living
Property component and catalyst gross mass ratio), catalyst carrier is cerium oxide, and it is three hydroxyls containing dopamine of 15wt% to add concentration
Aminomethane cushioning liquid, catalyst is 1 with the mass ratio of solution:7.Magnetic agitation 24h, then by suspension centrifugation point
From, thing is precipitated, then described sediment is adopted and is washed with deionized 3 times, then cleaned with ethanol 3 times；To remove
Contamination precipitation thing is vacuum dried at 120 DEG C, obtains monatomic catalyst Ag- poly-dopamines.
(3) annealing temperature be 900 DEG C, annealing rate be 8 DEG C/min, under conditions of the annealing time is 3h, will be single
Catalyst atom Ag- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Ag- carbon shells.
(4) the monatomic catalyst Ag- carbon shell that will be obtained calcines 3h in 800 DEG C of air atmospheres, the carbon shell of burning-off parcel,
Obtain through the amine-modified monatomic catalyst Ag of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 6000mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Ag of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 7 is through the amine-modified monatomic catalyst Ag catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 30 | 99.5 |
| 20 | 31 | 99.5 |
| 30 | 34 | 99.4 |
| 40 | 35 | 99.4 |
| 50 | 39 | 99.3 |
| 60 | 40 | 99.3 |
Table 8 is without the amine-modified monatomic catalyst Ag catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 10 | 99.8 |
| 20 | 21 | 99.6 |
| 30 | 178 | 97.0 |
| 40 | 374 | 93.8 |
| 50 | 645 | 89.2 |
| 60 | 942 | 84.3 |
Control after the amine-modified monatomic catalyst Ag continuous processings 60h of DOPA as can be seen that using still having more than
What remarkable activity, catalytic performance almost change without, and the monatomic catalyst Ag amine-modified for being provided without DOPA, when anti-
It is decreased obviously more than catalytic performance after 20h between seasonable, outlet VOCs concentration substantially rises, it is impossible to reach effective degradation effect.With
Upper result illustrates that the present invention can effectively extend service life of the monatomic catalyst in combustion degradation VOCs systems are catalyzed, tool
There is commercial application potentiality.
Embodiment 5
(1) preparation of the TRIS buffer containing dopamine.Trishydroxymethylaminomethane 2.0g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl ammonia that concentration is 2wt%
Methylmethane cushioning liquid.50mL solution is taken, 1.5g dopamines are added, the trihydroxy methyl containing dopamine that concentration is 3wt% is made into
Aminomethane buffer solution.
(2) monatomic catalyst-poly-dopamine is prepared.The monatomic catalyst Pt of 1g is taken, load capacity is 0.5wt% (living
Property component and catalyst gross mass ratio), catalyst carrier is concave convex rod, and it is three hydroxyls containing dopamine of 3wt% to add concentration
Aminomethane cushioning liquid, catalyst is 1 with the mass ratio of solution:1.Magnetic agitation 24h, then by suspension centrifugation point
From, thing is precipitated, then described sediment is adopted and is washed with deionized 3 times, then cleaned with ethanol 3 times；To remove
Contamination precipitation thing is vacuum dried at 60 DEG C, obtains monatomic catalyst Pt-poly-dopamine.
(3) annealing temperature be 400 DEG C, annealing rate be 2 DEG C/min, under conditions of the annealing time is 5h, will be single
Catalyst atom Pt- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Pt- carbon shells.
(4) the monatomic catalyst Pt-carbon shell that will be obtained calcines 10h, the carbon of burning-off parcel in 300 DEG C of air atmospheres
Shell, obtains through the amine-modified monatomic catalyst Pt of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 5200mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Pt of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 9 is through the amine-modified monatomic catalyst Pt catalytic performance test of DOPA
Table 10 is without the amine-modified monatomic catalyst Pt catalytic performance test of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 31 | 99.4 |
| 20 | 62 | 98.8 |
| 30 | 201 | 96.1 |
| 40 | 348 | 93.3 |
| 50 | 645 | 87.6 |
| 60 | 880 | 83.1 |
Control after the amine-modified monatomic catalyst Pt continuous processing 60h of DOPA as can be seen that using still having more than
Remarkable activity, catalytic performance only has to be reduced a little, and the monatomic catalyst Pt amine-modified for being provided without DOPA, when reacted
Between be decreased obviously more than catalytic performance after 20h, outlet VOCs concentration substantially rise, it is impossible to reach effective degradation effect.Tie above
Fruit illustrates that the present invention can effectively extend service life of the monatomic catalyst in combustion degradation VOCs systems are catalyzed, with work
Industry application potential.
Embodiment 6
(1) preparation of the TRIS buffer containing dopamine.Trishydroxymethylaminomethane 2.6g is taken, is added water
Then 100ml, stirring and dissolving adjusts pH value to 8.0 with 5mol/L hydrochloric acid solutions, obtains the trihydroxy methyl that concentration is 2.5wt%
Aminomethane buffer solution.50mL solution is taken, 12.5g dopamines are added, three hydroxyls containing dopamine that concentration is 20wt% are made into
Aminomethane cushioning liquid.
(2) monatomic catalyst-poly-dopamine is prepared.The monatomic catalyst Au of 1g is taken, load capacity is 1wt% (activity
Component and catalyst gross mass ratio), catalyst carrier is metal-organic framework materials, and addition concentration is 20wt% containing many
The trishydroxymethylaminomethane cushioning liquid of bar amine, catalyst is 1 with the mass ratio of solution:10.Magnetic agitation 24h, then will
Suspension centrifugation, is precipitated thing, then adopts described sediment and is washed with deionized 3 times, then clear with ethanol
Wash 3 times；Contamination precipitation thing will be removed to be vacuum dried at 150 DEG C, monatomic catalyst Au- poly-dopamines will be obtained.
(3) annealing temperature be 1200 DEG C, annealing rate be 8 DEG C/min, under conditions of the annealing time is 4h, will be single
Catalyst atom Au- poly-dopamines are made annealing treatment so that carbon shell parcel form catalyst atom, obtain monatomic catalyst
Au- carbon shells.
(4) the monatomic catalyst Au- carbon shell that will be obtained calcines 2h, the carbon of burning-off parcel in 1000 DEG C of air atmospheres
Shell, obtains through the amine-modified monatomic catalyst Au of DOPA.
The actual effect of catalyst is evaluated using existing catalysis burning evaluation method, reaction tube is quartz ampoule, and bore is
10mm, VOCs inlet concentrations are 5000mg/m3, wherein, benzene homologues account for 40%, and esters account for 35%, and alcohols accounts for 10%, and ethers is accounted for
The air speed of 15%, VOCs is 25000h-1, catalyst combustion reaction temperature is 300 DEG C.Using VOCs detector on-line checkings exit
The content of VOCs.It is anti-without catalysis burning has been also carried out using the amine-modified monatomic catalyst Au of DOPA for the ease of control
Should, comparing result is as shown in the table.
Table 11 is through the amine-modified monatomic catalyst Au catalytic performance tests of DOPA
Table 12 is without the amine-modified monatomic catalyst Au catalytic performance tests of DOPA
| Reaction time (h) | Clearance (%) | |
| 10 | 30 | 99.4 |
| 20 | 48 | 99.0 |
| 30 | 184 | 96.3 |
| 40 | 327 | 93.5 |
| 50 | 591 | 88.2 |
| 60 | 880 | 82.4 |
Control after the amine-modified monatomic catalyst Au continuous processings 60h of DOPA as can be seen that using still having more than
Remarkable activity, catalytic performance only has to be reduced a little, and the monatomic catalyst Au amine-modified for being provided without DOPA, when reacted
Between be decreased obviously more than catalytic performance after 20h, outlet VOCs concentration substantially rise, it is impossible to reach effective degradation effect.Tie above
Fruit illustrates that the present invention can effectively extend service lifes of the monatomic catalyst Au in combustion degradation VOCs systems are catalyzed, and has
Commercial application potentiality.
Claims (9)
1. a kind of method that raising is catalyzed the monatomic catalyst stability of burning VOCs, it is characterised in that comprise the following steps：
(1) TRIS buffer containing dopamine is prepared, is concretely comprised the following steps：Trishydroxymethylaminomethane is added water
Dilution is configured to the trishydroxymethylaminomethane cushioning liquid that concentration is 1-3wt%, is then adjusted pH value of buffer solution with hydrochloric acid
Save to 8.0, add dopamine, be made into the trishydroxymethylaminomethane cushioning liquid containing dopamine, described dopamine is containing
Concentration in the trishydroxymethylaminomethane cushioning liquid of dopamine is 3-20wt%；
(2) monatomic catalyst-poly-dopamine is prepared, is concretely comprised the following steps：
A monatomic catalyst is added the trishydroxymethylaminomethane cushioning liquid containing dopamine by (), be then sufficiently stirred for obtaining
Suspension；Described monatomic catalyst is 1 with the mass ratio of cushioning liquid:1~10, the load of described monatomic catalyst
It is 0.01-1wt% to measure；
B suspension centrifugation is precipitated thing by (), described sediment washing then is gone into the removal of impurity；
C () will remove contamination precipitation thing and be vacuum dried at 60-150 DEG C, obtain monatomic catalyst-poly-dopamine；
(3) annealing temperature be 400-1200 DEG C, annealing rate be 2-8 DEG C/min, annealing the time be 3-5h under conditions of,
Monatomic catalyst-poly-dopamine is made annealing treatment so that carbon shell parcel form catalyst atom, obtained monatomic catalysis
Agent-carbon shell；
(4) the monatomic catalyst-carbon shell that will be obtained calcines 2-10h in 300-1000 DEG C of air atmosphere, and burning-off is monatomic to urge
The carbon shell wrapped up in agent, obtains through the amine-modified monatomic catalyst of DOPA.
2. the method that raising according to claim 1 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：Concentration of the described dopamine in the trishydroxymethylaminomethane cushioning liquid containing dopamine is 7-15wt%.
3. the method that the raising according to claims 1 or 2 is catalyzed the monatomic catalyst stability of burning VOCs, it is special
Levy and be：Described monatomic catalyst is 1 with cushioning liquid mass ratio:4-7.
4. the method that raising according to claim 3 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：The load capacity of described monatomic catalyst is 0.01-0.2wt%.
5. the method that raising according to claim 4 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：The active component of described monatomic catalyst is any one in Pt, Pd, Au or Ag.
6. the method that raising according to claim 5 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：The carrier of described monatomic catalyst be alundum (Al2O3), ferroso-ferric oxide, titanium dioxide, cerium oxide, concave convex rod or
Any one in metal-organic framework materials.
7. the method that raising according to claim 6 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：Vacuum drying temperature is 80-120 DEG C.
8. the method that raising according to claim 6 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：Annealing temperature is 700-900 DEG C.
9. the method that raising according to claim 6 is catalyzed the monatomic catalyst stability of burning VOCs, its feature exists
In：Calcining heat is 500-800 DEG C, and calcination time is 3-6h.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233269A (en) * | 2010-04-26 | 2011-11-09 | 唐幸福 | Integral nano material with high-efficiency removing formaldehyde at room temperature and broad-spectrum long-acting antibacterial property at same time |
| CN102284077A (en) * | 2010-06-18 | 2011-12-21 | 上海牛翼新能源科技有限公司 | Multifunctional high-efficiency air purifier for indoor (vehicle) environment |
| CN104174411A (en) * | 2014-07-07 | 2014-12-03 | 中国科学院过程工程研究所 | Method for improving catalytic oxidization activity of VOCs catalyst |
-
2017
- 2017-04-02 CN CN201710215260.4A patent/CN106914278A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233269A (en) * | 2010-04-26 | 2011-11-09 | 唐幸福 | Integral nano material with high-efficiency removing formaldehyde at room temperature and broad-spectrum long-acting antibacterial property at same time |
| CN102284077A (en) * | 2010-06-18 | 2011-12-21 | 上海牛翼新能源科技有限公司 | Multifunctional high-efficiency air purifier for indoor (vehicle) environment |
| CN104174411A (en) * | 2014-07-07 | 2014-12-03 | 中国科学院过程工程研究所 | Method for improving catalytic oxidization activity of VOCs catalyst |
Non-Patent Citations (4)
| Title |
|---|
| 《空气和废气监测分析方法指南》编委会: "《空气和废气监测分析方法指南》", 31 July 2014, 中国环境出版社 * |
| WANGCHENG ZHAN ET AL.: "A Sacrificial Coating Strategy Toward Enhancement of Metal-Support Interaction for Ultrastable Au Nanocatalysts", 《J.AM.CHEM.SOC.》 * |
| 贲长恩等: "《组织化学》", 30 November 2001, 人民卫生出版社 * |
| 陈雅欣等: "单原子金属催化剂低温氧化甲醛的研究", 《第十九届SO2、NOX、PM2.5、HG污染防治技术研讨会论文集》 * |
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| CN108998113A (en) * | 2018-06-14 | 2018-12-14 | 安徽大学 | A kind of monatomic cobalt-based methanol fuel and preparation method thereof |
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