CN105032409A - Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof - Google Patents

Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof Download PDF

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CN105032409A
CN105032409A CN201510387563.5A CN201510387563A CN105032409A CN 105032409 A CN105032409 A CN 105032409A CN 201510387563 A CN201510387563 A CN 201510387563A CN 105032409 A CN105032409 A CN 105032409A
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ruthenium
catalyst
vocs
self
solution
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朱廷钰
王健
刘霄龙
王雪
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Institute of Process Engineering of CAS
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Abstract

The invention relates to a self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and a preparation method and applications thereof. According to the preparation method, rutile titania is adopted as a carrier, and ruthenium nano particle is taken as the active ingredient. The preparation method comprises following steps: firstly, ruthenium nano particle is synthesized in a liquid phase; the carrier is added, and pH value is adjusted so as to obtain the self-assembled nano ruthenium catalyst via complete absorption of the ruthenium nano particle onto the carrier. Compared with catalysts obtained via conventional impregnation-calcination, activity of the self-assembled nano ruthenium catalyst is higher; rutile titania is taken as the carrier, so that thermal stability of the self-assembled nano ruthenium catalyst is increased greatly, complete oxidation temperature of a plurality of VOCs ranges from 160 to 250 DEG C, and application prospect is promising.

Description

Self-assembled nanometer ruthenium catalyst, the preparation method and its usage of a kind of catalytic oxidation VOCs
Technical field
The invention belongs to resource and environment technical field, relate to a kind of supported ruthenium catalyst, preparation method and its usage, be specifically related to the self-assembled nanometer ruthenium catalyst of a kind of catalytic oxidation VOCs, preparation method and its usage, described catalyst adopts ruthenium nano-particle as active component, carrier is red schorl phase titanium dioxide, catalyst adopts previously prepared ruthenium nano-particle and the method synthesis of absorption deposition, make active component ruthenium with the fractions distribution of the best at carrier surface, and red schorl phase titanium dioxide effectively raises the stability of catalyst as carrier, can the multiple VOCs of efficient removal.
Background technology
Volatile organic matter (VolatileOrganicCompounds is called for short VOCs) kind is extremely many, and common comprises triphen (benzene, toluene and dimethylbenzene), chlorobenzene, trichloro-ethylene and ethyl acetate etc.Due to the development of modern industry, be chronically exposed to during VOCs pollutes the health problem caused and constantly occur.Be in for a long time in the environment that VOCs exceeds standard, can slow poisoning be caused, infringement liver, kidney and nervous system.VOCs is a kind of pollutant ball ecological environment being produced to quite large harm simultaneously, and the VOCs of such as large concentration can form photochemical fog, and some common VOCs gases are as methane, also have sizable contribution to global warming.From the VOCs emission problem that China is current, while strict control VOCs produces source, the end treatment of VOCs discharge also to be strengthened.
In lower temperature range, catalytic oxidation decomposition is carried out to VOCs species by catalytic oxidation, make VOCs species become CO 2and H 2substantially the free of contamination small-molecule substance such as O is a kind of VOCs control technology of very energy-saving and environmental protection.Catalytic oxidation technologies can realize the decomposition completely of VOCs pollutant in the temperature range of 150 ~ 500 DEG C, lower for VOCs concentration of emission, but the species that toxicity is large, such as the pollutant such as benzene, toluene has good control effects equally.
In recent years, the catalytic oxidation character of ruthenium element is received day by day to the concern of scientific research personnel.Find through research, ruthenium, in the catalyst system and catalyzing of oxygen content higher (such as oxygen is more than 1vol.%), forms RuO 2or a kind of metal Ru is to RuO 2a kind of transition state species in transition process, these ruthenium kind species are highly susceptible to absorption VOCs pollutant, have again the ability of stronger release oxygen simultaneously, thus have very high catalytic oxidation activity.Ruthenium is as the one of noble metal, and its price is but far below platinum, palladium.Therefore, exploitation one is based on ruthenium as active component, and the catalyst system having stronger catalytic capability for multiple VOCs pollutant has very important using value.
Summary of the invention
For the problem of prior art, an object of the present invention is the ruthenium catalyst providing a kind of catalytic oxidation VOCs, and described catalyst takes full advantage of the catalytic oxidation activity of ruthenium and has higher heat endurance.
To achieve these goals, present invention employs following technical scheme:
The self-assembled nanometer ruthenium catalyst of a kind of catalytic oxidation VOCs, comprise carrier and active component, described carrier is red schorl phase titanium dioxide, active component is ruthenium nano-particle, in the quality of catalyst for 100wt.%, described active component ruthenium nano-particle accounts for the mass percent≤5wt.% of catalyst.
Catalyst of the present invention adopts previously prepared ruthenium nano-particle colloidal sol and absorption is deposited on method synthesis (i.e. colloidal sol sedimentation) on carrier, makes active component better in the distribution of carrier surface.The carrier of catalyst is red schorl phase titanium dioxide with low cost, the RuO that ruthenium nano-particle is formed under excess oxygen 2have identical cell configuration with red schorl phase titanium dioxide, the two combination is very stable, thus significantly improves the heat endurance of catalyst.Gained catalyst of the present invention all has higher catalytic activity when the multiple VOCs of catalytic oxidation, and has very strong anti-fluorine poisoning ability when catalytic oxidation Cl-VOCs.
The mass percent that described active component ruthenium nano-particle accounts for catalyst is such as 0.2wt.%, 0.4wt.%, 0.6wt.%, 0.8wt.%, 1.0wt.%, 1.2wt.%, 1.4wt.%, 1.6wt.%, 1.8wt.%, 2.0wt.%, 3.0wt.%, 4.0wt.% or 5.0wt.%.When ruthenium content is 0.2 ~ 1.5wt.%, along with ruthenium load capacity increases, catalytic activity constantly raises; As ruthenium nano-particle content > 1.5wt.%, along with ruthenium load capacity increases, catalytic activity without significant change, from saving catalyst preparation materials cost consideration preferred 1.0wt.%.
The self-assembled nanometer ruthenium catalyst of exemplary a kind of catalytic oxidation VOCs, comprise carrier and active component, described carrier is red schorl phase titanium dioxide, active component is ruthenium nano-particle, in the quality of catalyst for 100wt.%, described carrier quality is 99wt.%, and the mass percent that described active component ruthenium nano-particle accounts for catalyst is 1.0wt.%.This catalyst is 180 DEG C to benzene complete oxidation temperature, the complete oxidation temperature of toluene is 200 DEG C, ortho-xylene complete oxidation temperature is 215 DEG C, phenol complete oxidation temperature 160 DEG C, and chlorobenzene complete oxidation temperature is 250 DEG C, 2-chlorophenol complete oxidation temperature is 185 DEG C, trichloro-ethylene complete oxidation temperature is 230 DEG C, and ethyl acetate complete oxidation temperature is 215 DEG C, and acetaldehyde complete oxidation temperature is 175 DEG C, propane complete oxidation temperature is 200 DEG C, and reaction end product CO 2selective>=99.5%, generates without CO substantially.
Two of object of the present invention is the preparation method of the self-assembled nanometer ruthenium catalyst providing a kind of catalytic oxidation VOCs as above, described method is sol deposition method, comprises and adopts sol method to prepare ruthenium nano-particle and by the step of its uniform deposition on carrier.
Said method comprising the steps of:
(1) in ruthenium precursor water solution, add polyvinyl alcohol (PVA), after it dissolves completely, under agitation in this solution, add NaBH rapidly 4solution, forms ruthenium nano-particle colloidal sol;
(2) pH of mixed liquor that obtains of regulating step (1), backward mixed liquor in add carrier, through leaving standstill, ruthenium nano-particle loaded body adsorbs, and obtain the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs, it is powder shaped.
Preferably, described method also comprise the supernatant liquor in the mixed liquor of clarification obtained after leaving standstill removed, filter, the step of washing and drying.
Preferably, described ruthenium presoma is RuCl 3or Ru (NO) (NO 3) 2, consider preferred RuCl from cost-saving angle 3;
Preferably, in the quality of ruthenium, the concentration of ruthenium precursor solution is 25 ~ 100mg/L, such as 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, 60mg/L, 65mg/L, 70mg/L, 75mg/L, 80mg/L, 85mg/L, 90mg/L, 95mg/L or 100mg/L, preferred 40mg/L.
Preferably, the weight average molecular weight of described polyvinyl alcohol (PVA) is 8000 ~ 10000g/mol.
Preferably, use PVA as the stabilizing agent in solution reduction process, the mass ratio of PVA and ruthenium element is 1:1-5:1, such as 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1,4:1,4.5:1 or 5:1.PVA and ruthenium ratio is in the solution too low, then in reduction process, ruthenium is easily reunited, and the too high meeting of ratio makes the ruthenium nano-particle generated diminish, and affects catalyst stability, is therefore preferably 2:1.
Preferably, NaBH is used 4as reducing agent, NaBH 4be 3:1-10:1, such as 3:1,4:1,5:1,6:1,7:1,8:1,9:1 or 10:1 with the mol ratio of ruthenium element, NaBH 4cause ruthenium cannot by Restore All with the too low meeting of the mol ratio of ruthenium, and the excessive too high larger-size ruthenium nano-particle that can be formed of ratio, even form ruthenium precipitation, be therefore preferably 5:1.
Preferably, described NaBH 4the concentration of solution is 0.01-0.5mol/L, is preferably 0.1mol/L.
The present invention uses aqueous phase as solvent phase in preparation process, and adopts NaBH 4reduce to ruthenium presoma in room temperature, preparation cost is low.
Preferably, by step (1) obtain mixed liquor pH be adjusted to 6.0 ~ 8.5 (such as 6.0,6.1,6.2,6.3,6.4,6.5,6.6,6.7,6.8,6.9,7.0,7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4 or 8.5), ruthenium nano-particle within the scope of this pH in solution is more easily adsorbed by rutile titanium dioxide, and preferably 7.0.
Preferably, the NaOH solution of HCl or 0.1mol/L of 0.1mol/L is used to regulate pH.
Preferably, 12 ~ 36h is left standstill in step (2), such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h or 36h, time of repose is too short, and ruthenium nano-particle cannot be adsorbed completely, therefore preferred 24h.
Preferably, adopt deionized water washing, remove the solubility salts substances of catalyst surface.
Preferably, powder washing obtained, at 110 DEG C of dry 6h, obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
Preferably, the preparation method of the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs is sol deposition method, comprises the steps:
(1) to RuCl 3add PVA (PVA weight average molecular weight is 8000 ~ 10000g/mol) in the aqueous solution, after it dissolves completely, in this solution, under agitation add rapidly the NaBH of 0.1mol/L 4solution;
(2) pH of the mixed liquor using the NaOH solution of HCl or 0.1mol/L of 0.1mol/L step (1) to be obtained is adjusted to 6.0 ~ 8.5, adds carrier afterwards, and through leaving standstill, ruthenium nano-particle loaded body adsorbs, and obtains the mixed liquor clarified;
(3) supernatant liquor of mixed liquor that obtains of removal step (2), filters, and with distilled water washing, afterwards by the powder that obtains at 110 DEG C of dry 6h, obtain the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
Preferably, the preparation method of the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs is sol deposition method, comprises the steps:
(1) to the RuCl of 40mg/L 3be incorporated as the PVA (PVA weight average molecular weight is 8000 ~ 10000g/mol) of ruthenium element quality 2 times in solution (quality in ruthenium), after it dissolves completely, in this solution, under agitation add rapidly the NaBH of 0.1mol/L 4solution, wherein NaBH 4be 5:1 with the mol ratio of ruthenium element;
(2) pH of the mixed liquor using the NaOH solution of HCl or 0.1mol/L of 0.1mol/L step (1) to be obtained is adjusted to 7.0, add red schorl phase titanium dioxide carrier afterwards, its quality is 99 times of ruthenium element quality in mixed liquor, after leaving standstill 24h, ruthenium nano-particle loaded body adsorbs;
(3) mixed liquor (2) obtained filters after removing supernatant liquor, and washs more than 3 times with distilled water, afterwards the powder obtained is carried out drying at 110 DEG C, obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
Above-mentioned solid powdery catalyst, can make various planform according to the actual requirements, such as, catalyst can be made spherical, the graininess of different size size and cellular etc.
Three of object of the present invention is the purposes of the self-assembled nanometer ruthenium catalyst providing a kind of catalytic oxidation VOCs as above, described catalyst is used for the various VOCs of catalytic oxidation, the catalytic oxidation of multiple VOCs in industrial tail gas can be realized, especially come from the key industry that petrochemical industry, pharmacy, organic chemical industry etc. cause VOCs to pollute.
Compared with the prior art, the present invention has following beneficial effect:
(1) traditional catalyst adopts infusion process preparation; usual active component particles is not of uniform size; its form non-optimal; and the present invention is by adopting sol deposition method; the ruthenium nano-particle that preparation size is homogeneous in aqueous phase in advance; the skin of ruthenium nano-particle can be oxidized in actual use, the RuO of formation 2all there is higher catalytic activity when the multiple VOCs of catalytic oxidation.
(2) adopt red schorl phase titanium dioxide as the carrier of ruthenium nano-particle, due to the RuO that ruthenium nano-particle is formed under excess oxygen 2have identical cell configuration with red schorl phase titanium dioxide, make ruthenium species be difficult to migration, therefore catalyst heat endurance is very outstanding.
(3) compared with commercial load type platinum, palladium catalyst, catalyst cost of the present invention is lower, is 160 ~ 250 DEG C to multiple VOCs complete oxidation temperature, reaction end product CO 2selective>=99.5%, substantially generate without CO, and this catalyst is high to Cl-VOCs catalytic oxidation stability such as chlorobenzenes, the air containing 500ppm chlorobenzene is carried out one-week catalytic oxidation test show, the conversion ratio of chlorobenzene fluctuates between 97.5-98.7%, do not observe any catalysqt deactivation phenomenon, there is good application prospect.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below by detailed description of the invention.
Embodiment 1
The catalyst of a kind of catalytic oxidation VOCs, comprise carrier and active component, described carrier is red schorl phase titanium dioxide, and active component is ruthenium nano-particle, in the quality of catalyst for 100wt.%, the mass percent that active component ruthenium nano-particle accounts for catalyst is 1wt.%.
Above-mentioned catalyst adopts sol deposition method, comprises the steps:
(1) to the RuCl of 40mg/L 3be incorporated as the PVA (PVA weight average molecular weight is 8000 ~ 10000g/mol) of ruthenium element quality 2 times in solution (quality in ruthenium), after it dissolves completely, in this solution, under agitation add rapidly the NaBH of freshly prepd 0.1mol/L 4solution, wherein NaBH 4be 5:1 with the mol ratio of ruthenium element;
(2) pH of the mixed liquor using the NaOH solution of HCl or 0.1mol/L of 0.1mol/L step (1) to be obtained is adjusted to 7.0, add red schorl phase titanium dioxide carrier afterwards, its quality is 99 times of ruthenium element quality in mixed liquor, after leaving standstill 24h, ruthenium nano-particle loaded body adsorbs;
(3) mixed liquor (2) obtained filters after removing supernatant liquor, and washs more than 3 times with distilled water, afterwards the powder obtained is carried out drying at 110 DEG C, obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
The complete oxidation temperature of this catalyst to benzene and chlorobenzene is respectively 180 DEG C and 250 DEG C, CO 2selective>=99.5%.
Embodiment 2
The mass percent accounting for catalyst except active component ruthenium nano-particle is except 0.2wt.%, and all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 245 DEG C, CO 2selective is>=99.5%.
Embodiment 3
The mass percent accounting for catalyst except active component ruthenium nano-particle is except 5wt.%, and all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 210 DEG C, CO 2selective is>=99.5%.
Embodiment 4
Except PVA addition and ruthenium element mass ratio are except 1:1, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 235 DEG C, CO 2selective is>=99.5%.
Embodiment 5
Except PVA addition and ruthenium element mass ratio are except 5:1, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 225 DEG C, CO 2selective is>=99.5%.
Embodiment 6
Except NaBH 4addition and ruthenium element mol ratio are outside 3:1, and all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 190 DEG C, CO 2selective is>=99.5%.
Embodiment 7
Except NaBH 4addition and ruthenium element mole ratio are for outside 10:1, and all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 240 DEG C, CO 2selective is>=99.5%.
Embodiment 8
Be adjusted to except 6.0 except by pH, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 190 DEG C, CO 2selective is>=99.5%.
Embodiment 9
Be adjusted to except 8.5 except by pH, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 195 DEG C, CO 2selective is>=99.5%.
Embodiment 10
Except the time of repose after adding carrier is except 12h, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 195 DEG C, CO 2selective is>=99.5%.
Embodiment 11
Except the time of repose after adding carrier is except 36h, all the other are identical with embodiment 1.
The complete oxidation temperature of catalyst to benzene is 180 DEG C, CO 2selective is>=99.5%.
Comparative example 1
Catalyst adopts ruthenium as active component, and carrier is red schorl phase titanium dioxide, and adopt common infusion process preparation, sintering temperature is 350 DEG C, and ruthenium content is identical with embodiment 1, and the complete oxidation temperature of this catalyst to benzene and chlorobenzene is respectively 220 DEG C and 275 DEG C.
Comparative example 2
Except employing anatase titania is as except carrier, all the other are identical with embodiment 1, the complete oxidation temperature of this catalyst to benzene and chlorobenzene is respectively 190 DEG C and 260 DEG C, but sinters in the process of catalytic oxidation VOCs due to ruthenium species, and catalyst stability is not good.
Comparative example 3
Catalyst adopts platinum as active component, and carrier is alundum (Al2O3), and in the quality of catalyst for 100wt.%, the mass percent that platinum accounts for catalyst is 1.0wt.%.The complete conversion temperature of this catalyst to benzene and chlorobenzene is 190 DEG C and 365 DEG C, and has occurred deactivation phenomenom in the catalytic oxidation of chlorobenzene.
Comparative example 4
Catalyst adopts single active component manganese oxide, and carrier is anatase titania, and in the quality of catalyst for 100wt.%, the mass percent that manganese oxide accounts for catalyst is 5.0wt.% (in mangano-manganic oxide).The complete conversion temperature of this catalyst to benzene is 310 DEG C.
Comparative example 5
Catalyst adopts single active component manganese oxide, and carrier is anatase titania, and in the quality of catalyst for 100wt.%, the mass percent that manganese oxide accounts for catalyst is 5.0wt.% (in mangano-manganic oxide).There is fluorine poisoning in the catalytic reaction of this catalyst to chlorobenzene, activity can not maintain.
Comparative example 6
Catalyst adopts the mixed oxide of manganese oxide (using mangano-manganic oxide) and ceria as active component, and in the quality of catalyst for 100wt.%, the mass percent that manganese oxide accounts for catalyst is 50wt.%.The complete conversion temperature of this catalyst to benzene is 280 DEG C.
Comparative example 7
Catalyst adopts the mixed oxide of manganese oxide (using mangano-manganic oxide) and ceria as active component, and in the quality of catalyst for 100wt.%, the mass percent that manganese oxide accounts for catalyst is 50wt.%.There is fluorine poisoning in the catalytic reaction of this catalyst to chlorobenzene, activity can not maintain at low temperature, and only when temperature just can show certain stability higher than 350 DEG C, and the complete conversion temperature of chlorobenzene is higher than 400 DEG C.
Known by the contrast of embodiment 1 and comparative example 1, owing to adopting the previously prepared ruthenium nano-particle of size uniformity of sol method, make the good dispersion degree of active component, catalyst activity high, and adopt the catalyst that traditional infusion process obtains, lower to the catalytic activity of common VOCs.
Known by the contrast of embodiment 1 and comparative example 2, owing to adopting red schorl phase titanium dioxide as carrier, ruthenium nano-particle is not easily moved in catalytic oxidation VOCs process, catalyst stability is good, and the catalyst heat endurance adopting anatase titania to obtain as carrier is poor.
Simultaneously, known by the global alignment of embodiment and comparative example, adopt ruthenium nano-particle to be significantly better than the catalyst of other active components or carrier as the catalytic activity of the catalyst of carrier and anti-fluorine poisoning performance as active component and red schorl phase titanium dioxide.
In addition, the present invention adopts water as solvent phase, NaBH 4as the reducing agent of ruthenium, with low cost.The present invention simultaneously passes through the content to active component ruthenium, stabilizing agent PVA and reducing agent NaBH 4adding proportion and carrier the absorption pH of ruthenium nano-particle and time are optimized, make ruthenium nano-particle activity higher, carrier to active component close to completely adsorb (> 99.9%).Catalyst prepared by this method can realize the complete oxidation of benzene in the temperature window of 180-245 DEG C.Best catalyst system (embodiment 1) the complete oxidation temperature to toluene, dimethylbenzene, chlorobenzene, phenol, 2-chlorophenol, ethyl acetate, acetaldehyde, propane is 160 ~ 250 DEG C, CO 2selective>=99.5%, and still can keep its catalytic stability when catalytic oxidation chlorobenzene.
To sum up, the catalyst system described in the present invention cost compared with the noble metal catalyst systems such as traditional platinum, palladium is lower; More obvious with the advantage that conventional transition metal oxide catalyst phase specific catalytic activity is high, and there is very strong anti-fluorine poisoning performance.
In the embodiment provided and comparative example, to the condition that catalyst is evaluated be:
Reactor: fixed-bed micro-reactor, reaction tube is internal diameter 4mm quartz ampoule;
Range of reaction temperature: 100 ~ 450 DEG C;
System pressure: 1 ~ 1.05atm;
Catalyst quality: 100mg;
Reaction velocity: 60000mLg -1h -1;
Organic concentration: 1000ppm;
Oxygen content: 20vol.%.
The import and export concentration of reactant and CO 2growing amount carry out on-line measurement by gas-chromatography.
For benzene, its conversion ratio and CO 2optionally be defined as:
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. the self-assembled nanometer ruthenium catalyst of a catalytic oxidation VOCs, comprise carrier and active component, described carrier is red schorl phase titanium dioxide, active component is ruthenium nano-particle, in the quality of catalyst for 100wt.%, described active component ruthenium nano-particle accounts for the mass percent≤5wt.% of catalyst.
2. catalyst as claimed in claim 1, it is characterized in that, the mass percent that described active component ruthenium nano-particle accounts for catalyst is 0.2 ~ 5.0wt.%, preferred 1.0wt.%.
3. a preparation method for the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs as claimed in claim 1 or 2, described method is sol deposition method, comprises and adopts sol method to prepare ruthenium nano-particle and be deposited on the step on carrier.
4. method as claimed in claim 3, is characterized in that, said method comprising the steps of:
(1) in ruthenium precursor water solution, add polyvinyl alcohol (PVA), after it dissolves completely, under agitation in this solution, add NaBH rapidly 4solution, forms ruthenium nano-particle colloidal sol;
(2) pH of mixed liquor that obtains of regulating step (1), then in mixed liquor, add carrier, through leaving standstill, ruthenium nano-particle loaded body adsorbs, and obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
5. method as claimed in claim 4, is characterized in that, described method also comprise the supernatant liquor in the mixed liquor obtained after leaving standstill removed, filter, the step of washing and drying.
6. the method as described in claim 4 or 5, is characterized in that, described ruthenium presoma is RuCl 3or Ru (NO) (NO 3) 2, preferred RuCl 3;
Preferably, in the quality of ruthenium element, in ruthenium precursor water solution, the concentration of ruthenium is 25 ~ 100mg/L, preferred 40mg/L;
Preferably, the weight average molecular weight of described PVA is 8000 ~ 10000g/mol;
Preferably, the mass ratio of PVA and ruthenium element is 1:1-5:1, is preferably 2:1.
7. the method as described in one of claim 4-6, is characterized in that, NaBH 4be 3:1-10:1 with the mol ratio of ruthenium element, be preferably 5:1;
Preferably, described NaBH 4the concentration of solution is 0.01-0.5mol/L, preferred 0.1mol/L.
8. the method as described in one of claim 4-7, is characterized in that, by step (1) obtain mixed liquor pH be adjusted to 6.0 ~ 8.5, preferably 7.0;
Preferably, the NaOH solution of HCl or 0.1mol/L of 0.1mol/L is adopted to carry out the adjustment of pH;
Preferably, in step (2), leave standstill 12 ~ 36h, preferably leave standstill 24h;
Preferably, powder washing obtained, at 110 DEG C of dry 6h, obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
9. the method as described in one of claim 3-8, is characterized in that, described method comprises the steps:
(1) to RuCl 3add PVA (PVA weight average molecular weight is 8000 ~ 10000g/mol) in the aqueous solution, after it dissolves completely, in this solution, under agitation add rapidly the NaBH of 0.1mol/L 4solution;
(2) pH of the mixed liquor using the NaOH solution of HCl or 0.1mol/L of 0.1mol/L step (1) to be obtained is adjusted to 6.0 ~ 8.5, adds carrier afterwards, and through leaving standstill, ruthenium nano-particle loaded body adsorbs, and obtains the mixed liquor clarified;
(3) supernatant liquor of mixed liquor that obtains of removal step (2), filters, and with distilled water washing, afterwards by the powder that obtains at 110 DEG C of dry 6h, obtain the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs;
Preferably, described method comprises the steps:
(1) to the RuCl of 40mg/L 3be incorporated as the PVA (PVA weight average molecular weight is 8000 ~ 10000g/mol) of ruthenium element quality 2 times in solution (quality in ruthenium), after it dissolves completely, in this solution, under agitation add rapidly the NaBH of 0.1mol/L 4solution, wherein NaBH 4be 5:1 with the mol ratio of ruthenium element;
(2) pH of the mixed liquor using the NaOH solution of HCl or 0.1mol/L of 0.1mol/L step (1) to be obtained is adjusted to 7.0, add red schorl phase titanium dioxide carrier afterwards, its quality is 99 times of ruthenium element quality in mixed liquor, after leaving standstill 24h, ruthenium nano-particle loaded body adsorbs;
(3) mixed liquor (2) obtained filters after removing supernatant liquor, and washs more than 3 times with distilled water, afterwards the powder obtained is carried out drying at 110 DEG C, obtains the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs.
10. a purposes for the self-assembled nanometer ruthenium catalyst of catalytic oxidation VOCs as claimed in claim 1 or 2, described catalyst is used for the various VOCs of catalytic oxidation.
CN201510387563.5A 2015-07-03 2015-07-03 Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof Pending CN105032409A (en)

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CN108212149A (en) * 2017-04-22 2018-06-29 天津大学 High dispersive type ruthenium oxide catalysts and its preparation method and application
CN108906044A (en) * 2018-06-15 2018-11-30 中国科学院过程工程研究所 A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application
CN108906044B (en) * 2018-06-15 2021-01-05 中国科学院过程工程研究所 Manganese-cerium-ruthenium composite oxide catalyst and preparation method and application thereof
CN109289843A (en) * 2018-11-01 2019-02-01 中国科学院长春应用化学研究所 Catalyst, preparation method and application is precipitated in sea urchin shape rutile titanium dioxide ruthenium oxide loaded body oxygen
CN109289843B (en) * 2018-11-01 2020-07-07 中国科学院长春应用化学研究所 Sea urchin-shaped rutile type titanium dioxide supported ruthenium oxide oxygen precipitation catalyst, and preparation method and application thereof
CN110433800A (en) * 2019-08-23 2019-11-12 河北工业大学 A kind of preparation and application of the load ruthenium catalyst with crystal face effect
CN110433800B (en) * 2019-08-23 2020-04-03 河北工业大学 Preparation and application of supported ruthenium catalyst with crystal face effect
CN112547059A (en) * 2020-09-07 2021-03-26 北京工业大学 Ru/3DOM SnO with good stability2Preparation method and application of catalyst
CN112547059B (en) * 2020-09-07 2024-01-26 北京工业大学 Ru/3DOM SnO with good stability 2 Preparation method and application of catalyst

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