CN105195139B

CN105195139B - A kind of ruthenium catalyst, preparation method and its usage for catalysis oxidation VOCs

Info

Publication number: CN105195139B
Application number: CN201510665019.2A
Authority: CN
Inventors: 朱廷钰; 王健; 刘霄龙; 曾俊淋
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2015-10-15
Filing date: 2015-10-15
Publication date: 2017-12-26
Anticipated expiration: 2035-10-15
Also published as: CN105195139A

Abstract

The present invention relates to a kind of load type metal catalyst, preparation method and its usage for catalysis oxidation VOCs.The catalyst uses red schorl phase titanium dioxide as carrier, and uses Al to carrier₂O₃Or La₂O₃Modified, active component is the oxide of ruthenium, and preparation method is equi-volume impregnating.The catalyst is modified carrier first in preparation process, carries out the load of active component afterwards.In the present invention particle size of the oxide of ruthenium after load is successfully controlled by carrier modify, and the migration path of ruthenium species has been effectively blocked it, not only make the oxide active of the ruthenium of carrier surface higher, and improve stability of the catalyst during long-term use simultaneously.For this catalyst system and catalyzing to a variety of VOCs complete catalysts oxidation temperature all between 165~250 DEG C, overall performance and stability have preferable application prospect better than the catalyst system without carrier modification.

Description

A kind of ruthenium catalyst, preparation method and its usage for catalysis oxidation VOCs

Technical field

The invention belongs to resource and environment technical field, is related to a kind of supported ruthenium catalyst, preparation method and its use On the way, and in particular to a kind of a variety of VOCs of catalysis oxidation catalyst, preparation method and its usage.The catalyst uses the oxygen of ruthenium Compound plays a supportive role as active component, carrier rutile titanium dioxide to the oxide of ruthenium, and carrier is by modification, modification group It is divided into Al₂O₃Or La₂O₃, it not only limit the granular size of the oxide of ruthenium, while to the oxide of ruthenium in carrier surface Migration serves the effect of obstruction.Therefore, the activity of catalyst and stability get a promotion, can a variety of VOCs of efficient removal.

Background technology

Volatile organic matter (Volatile Organic Compounds, abbreviation VOCs) is that a series of readily volatilized have The general designation of malicious harmful substance, extensive concern is caused due to its significant damage to human health.VOCs species is extremely more, long Phase is in environment exceeded VOCs, can cause slow poisoning, and the VOCs of big concentration can form photochemistry cigarette under light illumination Mist, terrestrial climate is caused to warm.There is clear and definite regulation in developed country for the VOCs pollutant emission limits of industry-by-industry, and China is also formulating detailed VOCs pollutant emission standards at present.The discharge that VOCs is controlled from source is no doubt having for row The measure of effect, but VOCs discharge is exceeded still inevitable in many industrial process.Therefore, end-of-pipe control VOCs's Discharge turns into the important ring for administering VOCs pollutions.

At present it has been reported that VOCs control technologies in, catalytic oxidation more saves relative to direct combustion method, ring Protect, VOCs pollutions can be directly eliminated relative to absorption method.Above-mentioned advantage causes catalytic oxidation to contain a variety of low concentrations in purification The waste gas of organic pollution has the advantage that can not be substituted.

Catalytic oxidation typically uses noble metal and transition metal oxide as active component, such as Pt, Pd, MnO_xWith CoO_xDeng.At present, developed country administers VOCs pollutions using catalytic oxidation and has been achieved with extraordinary effect, forms very big Social value.But common catalyst system and catalyzing still has some problems at present, such as precious metals pt/Pd relatively very high It is expensive so that the application of the high catalyst system and catalyzing of this activity is restricted.And transition metal oxide is with respect to noble metal Activity is poor, and is easy to that fluorine poisoning occurs.Therefore, development it is cheap, efficiently, universality is strong, stability is good (heat endurance and Anti- Poisoning) catalyst, it has also become catalytic oxidation administer industrial tail gas in VOCs pollutants key point.

The one kind of ruthenium as noble metal, relative low price.In recent years, the catalytic property of ruthenium is more and more closed Note.Not only activity is high for ruthenium, and fabulous catalytic capability is respectively provided with for multiple pollutant.But ruthenium lacking as active component Point easily migrates for it in carrier surface, causes the generation reunited, greatly reduces the quantity of avtive spot, reduce catalysis Activity.

The content of the invention

The problem of for prior art, an object of the present invention are the catalysis for providing a kind of a variety of VOCs of catalysis oxidation Agent, its have it is cheap, efficiently, universality is strong and the advantages of stability good (heat endurance and anti-Poisoning).

To achieve these goals, present invention employs following technical scheme：

A kind of catalysis oxidation VOCs catalyst, the catalyst include carrier and active component, and the carrier is golden red Stone phase titanic oxide, it is by modification, and the modification component used of modifying is Al₂O₃Or La₂O₃, active component is the oxygen of ruthenium Compound, counted using the quality of catalyst as 100wt.%, modification component accounts for mass percent≤10wt.% of catalyst, activearm The oxide of ruthenium is divided to account for mass percent≤5wt.% of catalyst (in terms of the quality of ruthenium).

The present invention is used as carrier from red schorl phase titanium dioxide, with very strong mutual between the oxide and carrier of ruthenium Effect, is tightly combined.Obvious Particle size effect during catalysis oxidation be present in the oxide of ruthenium, larger particle its Surface-active site it is active stronger.But in the case where the oxide carried amount of ruthenium is certain, with the oxide particle of ruthenium Increase, the quantity of integer catalyzer avtive spot reduces.Accordingly, there exist optimum particle size so that catalyst is overall Active highest.The present invention uses Al₂O₃Or La₂O₃Carrier is modified in advance as modification component, due to modification component and ruthenium Oxide between be difficult to combine, the content that component can be modified by adjusting adjust the granular size of the oxide of ruthenium, enter And catalyst is set to reach optimum state.Simultaneously because modification component generates cut-off to the migration path of active component, so as to carry Stability during high catalyst long-term use.Therefore, on the one hand the present invention causes ruthenium by modifying carrier Oxide more suitable granular size of self-assembling formation in preparation process, the oxide of ruthenium is on the other hand limited in carrier table The migration in face, serve the effect for improving catalyst activity and stability.Gained catalyst of the invention is a variety of in catalysis oxidation All there is higher catalytic activity and excellent heat endurance, activity is very high in catalysis oxidation chloro VOCs and has during VOCs Splendid anti-chlorine poisoning capability.

In the present invention, the oxide of the active component ruthenium accounted for (in terms of the quality of ruthenium) mass percent of catalyst≤ 5wt.%, for example, 0.2wt.%, 0.4wt.%, 0.6wt.%, 0.8wt.%, 1.0wt.%, 1.2wt.%, 1.4wt.%, 1.6wt.%, 1.8wt.%, 2.0wt.%, 2.5wt.%, 3.0wt.%, 3.5wt.%, 4.0wt.%, 4.5wt.% or 5.0wt.%, preferably 0.2~5.0wt.%.In general, when active component content is in the range of 0.2~2.0wt.%, with Load capacity increase, catalytic activity constantly raise；As active component content >=2.0wt.%, as load capacity increases, catalysis is lived Property without significant change, therefore from catalyst preparation materials cost consideration is saved, the oxide of preferably ruthenium accounts for (in terms of the quality of ruthenium) The mass percent of catalyst is 1.0wt.%.

In the present invention, the mass percent≤10wt.% for modifying component and accounting for catalyst, such as 1wt.%, 2wt.%, 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 9wt.% or 10wt.%, preferably 1~ 10wt.%.The catalytic activity of catalyst and the species (Al using modification component₂O₃Or La₂O₃) it is substantially unrelated, but with modification group The relation with contents divided is very big.In general, when modification constituent content is relatively low (such as≤2wt.%), it is difficult to active component ruthenium Oxide distribution produce significantly affect, and when modification constituent content it is too high (such as >=7wt.%), carrier surface can be caused Red schorl phase titanium dioxide exposed amount degradation, causes the oxide of active component ruthenium to be difficult to be firmly attached to carrier surface, Catalyst stability is caused to decline to a great extent, therefore, the mass percent that modification component accounts for catalyst is preferably 2~7wt.%.When Modification constituent content is moderate (such as ≈ 5wt.%), and catalyst surface had both exposed a considerable amount of red schorl phase titanium dioxides and has been The oxide of ruthenium provides attachment site, there is that considerable modification component limits its granular size and what may be occurred move again Move, now modification effect is good, and therefore, modification component accounts for the mass percent most preferably 5wt.% of catalyst.

A kind of exemplary catalysis oxidation VOCs catalyst, including carrier and active component, the carrier are rutile Phase titanic oxide, it is by modification, and the modification component used of modifying is Al₂O₃Or La₂O₃, active component is the oxidation of ruthenium Thing, counted using the quality of catalyst as 100wt.%, the mass percent that the modification component accounts for catalyst is 5wt.%, activearm The oxide (being counted using the quality of ruthenium) of ruthenium is divided to account for the mass percent of catalyst as 1wt.%.In addition, carrier surfactant component Distribution be it is optimal, and stability lifting it is the most obvious.With Al₂O₃The red schorl phase titanium dioxide load ruthenium of modification Exemplified by oxide catalyst, the mass percent that the modification component accounts for catalyst is 5wt.%, the oxide of active component ruthenium (being counted using the quality of ruthenium) accounts for the mass percent of catalyst as 1wt.%, and catalyst is 185 DEG C to benzene complete oxidation temperature, toluene Complete oxidation temperature be 200 DEG C, ortho-xylene complete oxidation temperature be 220 DEG C, 165 DEG C of phenol complete oxidation temperature, chlorobenzene Complete oxidation temperature is 250 DEG C, and 2- chlorophenol complete oxidations temperature is 195 DEG C, and trichloro ethylene complete oxidation temperature is 220 DEG C, Ethyl acetate complete oxidation temperature is 235 DEG C, and acetaldehyde complete oxidation temperature is 180 DEG C, and propane complete oxidation temperature is 190 DEG C, And reaction final product CO₂Selectivity >=99.5%, generated substantially without CO.

The second object of the present invention is to provide a kind of preparation method of catalysis oxidation VOCs as described above catalyst, Methods described is equi-volume impregnating, is comprised the following steps：

(1) red schorl phase titanium dioxide is mixed with the precursor water solution of aluminium or lanthanum, stood after stirring, Ran Houjin Row is dried and roasting, the carrier after being modified；

(2) carrier after the modification for obtaining step (1) is added in the precursor water solution of ruthenium, quiet after stirring Put, be then dried and be calcined, obtain catalysis oxidation VOCs catalyst.

Preferably, the presoma of aluminium is aluminum nitrate.

Preferably, the presoma of lanthanum is lanthanum nitrate.

Preferably, time of repose is 2~24h in step (1), for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 12h.

Preferably, drying time is 2~24h in step (1), for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 6h.

Preferably, sintering temperature is 400~600 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or 600 in step (1) DEG C, it is preferable that sintering temperature is 500 DEG C.

Preferably, roasting time is 2~24h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 6h.

Preferably, the presoma of step (2) described ruthenium is RuCl₃Or/and Ru (NO) (NO₃)₂, examined from cost-effective angle Consider preferred RuCl₃。

Preferably, time of repose is 2~24h in step (2), for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 12h.

Preferably, drying time is 2~24h in step (2), for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 6h.

Preferably, step (2) roasting temperature be 200~500 DEG C, such as 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C or 500 DEG C, sintering temperature is too low to be difficult to make ruthenium form stable structure, too high that ruthenium can be caused serious sintering occur, therefore Preferably 350 DEG C.

Preferably, roasting time is 2~24h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, preferably 4h.

The catalyst for the catalysis oxidation VOCs that the above method obtains is used as solid powdery.The solid powdery is catalyzed Agent, various planforms can be made according to the actual requirements, such as catalyst can be made to spherical, the graininess of different sizes With it is cellular etc..

The third object of the present invention is to provide a kind of purposes of catalysis oxidation VOCs as described above catalyst, described Catalyst is used for the various VOCs of catalysis oxidation, is such as used to be catalyzed a variety of non-chloros and chloro VOCs, can be achieved more in industrial tail gas Kind of VOCs catalysis oxidation, especially from the industries such as petrochemical industry, pharmaceutical industry, organic chemical industry, its tail gas VOCs contain Amount is generally higher, and species is various, is the key industry for causing VOCs to pollute.

Compared with the prior art, the present invention has the advantages that：

(1) present invention modifies by using red schorl phase titanium dioxide as carrier, and to carrier, carries out ruthenium afterwards Oxide load, due to by modification component limited, the oxide of ruthenium is obtained after dipping and roasting to be spontaneously formed Certain granular size, can by adjust modify component content and then adjust ruthenium oxide particle size size, from And improve the activity of catalyst.It is additionally, since modification component and has blocked the migration path of ruthenium so that catalyst not easy-sintering, makes Stability of the catalyst during long-term use is obtained to be significantly improved and (do not have activity decrease by 720h estimation of stabilitys). Catalyst system of the present invention has the advantages that catalytic activity is high, universality is strong, heat endurance is good, can urge a variety of VOCs Change is oxidized to CO₂And H₂The small molecule inorganic matter such as O, optimal catalyst are 165~250 DEG C to a variety of VOCs complete oxidations temperature, instead Answer final product CO₂Selectivity >=99.5%, generated substantially without CO.Moreover, the catalyst is to the Cl-VOCs catalysis oxidations such as chlorobenzene Stability is high, shows not to be catalyzed carrying out the air containing 500ppm chlorobenzenes one-week catalysis oxidation test Agent inactivates.

(2) active component of catalyst of the present invention is the oxide of ruthenium, prepare the raw material of catalyst and commercial load type platinum, Palladium catalyst is relatively low compared to cost, it is close to a variety of VOCs complete catalysts oxidation temperature or better than platinum, palladium catalyst 200~ 280 DEG C of temperature window, there is good application prospect.

Embodiment

Technical scheme is further illustrated below by embodiment.

Embodiment 1

A kind of catalysis oxidation VOCs catalyst, it is characterised in that the catalyst includes carrier and active component, described Carrier is red schorl phase titanium dioxide, and, by modification, modification component is Al for it₂O₃, active component is the oxide of ruthenium, with catalysis The quality of agent is counted for 100wt.%, the modification component Al₂O₃The mass percent for accounting for catalyst is 5.0wt.%, active component The oxide (being counted using the quality of ruthenium) of ruthenium accounts for the mass percent of catalyst as 1.0wt.%.

Above-mentioned catalyst is prepared using equi-volume impregnating, and it comprises the following steps：

(1) aluminum nitrate is dissolved into water, adds red schorl phase titanium dioxide afterwards and stir, obtain mixed serum, Roasting 6h for the first time are then carried out at 500 DEG C in 110 DEG C of dry 6h after standing 12h at room temperature；

(2) powder obtained by step (1) is added to RuCl₃In solution, stand after stirring, stand at room temperature In 110 DEG C of dry 6h after 12h, second of roasting 4h is then carried out at 350 DEG C, obtains catalysis oxidation VOCs catalyst.

Catalyst is respectively 185 DEG C and 250 DEG C to the complete oxidation temperature of benzene and chlorobenzene, CO₂Selectivity is >=99.5%, And activity does not decline after 720h estimation of stability.

Embodiment 2

In addition to the oxide (being counted using the quality of ruthenium) of active component ruthenium accounts for the mass percent of catalyst as 0.2wt.%, Remaining is same as Example 1.

Catalyst is 255 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 3

In addition to the oxide (being counted using the quality of ruthenium) of active component ruthenium accounts for the mass percent of catalyst as 10wt.%, Remaining is same as Example 1.

Catalyst is 220 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 4

Except modification component Al₂O₃The mass percent for accounting for catalyst is that remaining is same as Example 1 outside 1wt.%.

Embodiment 5

Except modification component Al₂O₃The mass percent for accounting for catalyst is that remaining is same as Example 1 outside 10wt.%.

Catalyst is 245 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 6

In addition to sintering temperature is 400 DEG C in step (1), remaining is same as Example 1.

Catalyst is 190 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 7

In addition to sintering temperature is 600 DEG C in step (1), remaining is same as Example 1.

Embodiment 8

In addition to sintering temperature is 200 DEG C in step (2), remaining is same as Example 1.

Catalyst is 200 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 9

In addition to sintering temperature is 500 DEG C in step (2), remaining is same as Example 1.

Embodiment 10

A kind of catalysis oxidation VOCs catalyst, it is characterised in that the catalyst includes carrier and active component, described Carrier is red schorl phase titanium dioxide, and, by modification, modification component is La for it₂O₃, active component is the oxide of ruthenium, with catalysis The quality of agent is counted for 100wt.%, and the mass percent that the modification component accounts for catalyst is 5.0wt.%, active component ruthenium Oxide (being counted using the quality of ruthenium) accounts for the mass percent of catalyst as 1.0wt.%.

(1) lanthanum nitrate is dissolved into water, adds red schorl phase titanium dioxide afterwards and stir, obtain mixed serum, Roasting 6h for the first time are then carried out at 500 DEG C in 110 DEG C of dry 6h after standing 12h at room temperature；

Catalyst is respectively 190 DEG C and 250 DEG C to the complete oxidation temperature of benzene and chlorobenzene, CO₂Selectivity is >=99.5%.

Embodiment 11

In addition to the oxide (being counted using the quality of ruthenium) of active component ruthenium accounts for the mass percent of catalyst as 0.2wt.%, Remaining is same as in Example 10.

Catalyst is 260 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 12

In addition to the oxide (being counted using the quality of ruthenium) of active component ruthenium accounts for the mass percent of catalyst as 10wt.%, Remaining is same as in Example 10.

Catalyst is 225 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 13

Except modification component La₂O₃The mass percent for accounting for catalyst is that remaining is same as in Example 10 outside 1wt.%.

Embodiment 14

Except modification component La₂O₃The mass percent for accounting for catalyst is that remaining is same as in Example 10 outside 10wt.%.

Embodiment 15

In addition to sintering temperature is 400 DEG C in step (1), remaining is same as in Example 10.

Catalyst is 195 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Embodiment 16

In addition to sintering temperature is 600 DEG C in step (1), remaining is same as in Example 10.

Embodiment 17

In addition to sintering temperature is 200 DEG C in step (2), remaining is same as in Example 10.

Embodiment 18

In addition to sintering temperature is 500 DEG C in step (2), remaining is same as in Example 10.

Catalyst is 250 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%.

Comparative example 1

The catalyst is using anatase phase titanium dioxide as carrier, and preparation process is same as Example 1, active component ruthenium Oxide (being counted using the quality of ruthenium) account for the mass percent of catalyst as 1wt.%.

Catalyst is 260 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity is >=99.5%, is commented by 24h stability Valency rear catalyst activity decrease, the complete conversion temperature of benzene is 290 DEG C.

Comparative example 2

The catalyst directly uses red schorl phase titanium dioxide as carrier, preparation process and step (2) phase in embodiment 1 Together, i.e., Al is not carried out to it₂O₃Modification, the oxide of active component ruthenium account for the mass percent of catalyst (in terms of the quality of ruthenium) For 1wt.%.

Catalyst is 220 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity was >=99.5%, by the activity of 720 hours Rear catalyst activity decrease is evaluated, the complete conversion temperature of benzene is 230 DEG C.

Comparative example 3

The catalyst uses single active component cobalt oxide (in terms of cobaltosic oxide), and carrier is red schorl phase titanium dioxide, Counted using the quality of catalyst as 100wt.%, the mass percent that cobalt oxide accounts for catalyst is 3.0wt.%.Catalyst is to benzene Complete oxidation temperature is 325 DEG C, CO₂Selectivity is >=99.5%.

Comparative example 4

The catalyst uses single active component cobalt oxide (in terms of cobaltosic oxide), and carrier is red schorl phase titanium dioxide, Counted using the quality of catalyst as 100wt.%, the mass percent that manganese oxide accounts for catalyst is 3.0wt.% (with mangano-manganic oxide Meter).Catalyst occurs fluorine poisoning to the catalytic reaction of chlorobenzene, and activity can not maintain.

Comparative example 5

The catalyst uses the mixed oxidization of manganese oxide (in terms of mangano-manganic oxide) and cobalt oxide (in terms of cobaltosic oxide) Thing is counted, the mass percent that manganese oxide accounts for catalyst is as active component using the quality of catalyst as 100wt.% 50wt.%.Catalyst is 290 DEG C to the complete conversion temperature of benzene.

Comparative example 6

The catalyst uses the mixed oxidization of manganese oxide (in terms of mangano-manganic oxide) and cobalt oxide (in terms of cobaltosic oxide) Thing is counted, the mass percent that manganese oxide accounts for catalyst is as active component using the quality of catalyst as 100wt.% 50wt.%.Catalyst occurs fluorine poisoning to the catalytic reaction of chlorobenzene, and activity can not maintain in low temperature, only when temperature is higher than 400 Certain stability DEG C can be just shown, and the complete conversion temperature of chlorobenzene is higher than 450 DEG C.

Comparative example 7

The catalyst is prepared using equi-volume impregnating, and it comprises the following steps：

Red schorl phase titanium dioxide is added to aluminum nitrate and RuCl₃In solution, stood after stirring, it is quiet at room temperature Put after 12h in 110 DEG C of dry 6h, then carry out roasting 6h at 350 DEG C, obtain catalysis oxidation VOCs catalyst.

Wherein, counted using the quality of catalyst as 100wt.%, Al₂O₃The mass percent for accounting for catalyst is 5.0wt.%, ruthenium Oxide (being counted using the quality of ruthenium) account for the mass percent of catalyst as 1.0wt.%.

Catalyst is 250 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity was >=99.5%, by the activity of 720 hours Evaluation rear catalyst activity does not decline.

Comparative example 8

Red schorl phase titanium dioxide is added to lanthanum nitrate and RuCl₃In solution, stood after stirring, it is quiet at room temperature Put after 12h in 110 DEG C of dry 6h, then carry out roasting 6h at 350 DEG C, obtain catalysis oxidation VOCs catalyst.

Wherein, counted using the quality of catalyst as 100wt.%, La₂O₃The mass percent for accounting for catalyst is 5.0wt.%, ruthenium Oxide (being counted using the quality of ruthenium) account for the mass percent of catalyst as 1.0wt.%.

Catalyst is 255 DEG C to the complete oxidation temperature of benzene, CO₂Selectivity was >=99.5%, by the activity of 720 hours Evaluation rear catalyst activity does not decline.

Above-described embodiment is contrasted to understand with comparative example：

The red schorl phase titanium dioxide for having strong effect between the oxide of ruthenium is not used as carrier, or not to gold Red stone phase titanic oxide is modified, and obtained catalyst system is lower than the active catalyst system described in the present invention, together When stability it is also poor.And use conventional load type transition metal oxide or transition metal oxide mixed catalyst body Occurs deactivation phenomenom during tying up to catalysis oxidation benzene, activity can not maintain, and its catalytic oxidation performance to benzene Well below load ruthenium catalyst system of the carrier described in the present invention by modification.Catalyst system in the present invention by In employing red schorl phase titanium dioxide as carrier, and carrier is modified, substantially increase the activity of catalyst And stability, and due to ruthenium oxide itself the characteristics of, its during the chloride VOCs of catalysis oxidation (such as chlorobenzene) not It can inactivate.In the present invention catalyst (embodiment 1) to benzene, toluene, ortho-xylene, chlorobenzene, phenol, 2- chlorophenols, ethyl acetate, Acetaldehyde, the complete oxidation temperature of propylene are 165~250 DEG C, CO₂Selectivity >=99.5%.

In the embodiment and comparative example provided, the condition evaluated catalyst is：

Reactor：Fixed-bed micro-reactor, reaction tube are internal diameter 4mm quartz ampoules；

Range of reaction temperature：100~350 DEG C；

System pressure：1~1.05atm；

Catalyst quality：100mg；

Reaction velocity：60000mL·g^-1·h^-1；

Organic concentration：1000ppm；

Oxygen content：20vol.%.

The inlet and outlet concentration and CO of reactant_xGrowing amount on-line measurement is carried out by gas-chromatography.

By taking benzene as an example, its conversion ratio and CO₂Selectivity definition be：

Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims

1. a kind of catalysis oxidation VOCs catalyst, the catalyst includes carrier and active component, and the carrier is rutile Phase titanic oxide, it is by modification, and the modification component used of modifying is Al₂O₃Or La₂O₃, active component is the oxidation of ruthenium Thing, counted using the quality of catalyst as 100wt.%, the mass percent that modification component accounts for catalyst is 2~7wt.%, activearm Divide the oxide of ruthenium, in terms of the quality of ruthenium, account for mass percent≤5wt.% of catalyst.

2. catalyst as claimed in claim 1, it is characterised in that the oxide of active component ruthenium, in terms of the quality of ruthenium, account for and urge The mass percent of agent is 0.2~5.0wt.%.

3. catalyst as claimed in claim 1, it is characterised in that the oxide of active component ruthenium, in terms of the quality of ruthenium, account for and urge The mass percent of agent is 1.0wt.%.

4. catalyst as claimed in claim 1, it is characterised in that modification component accounts for the mass percent of catalyst and is 5wt.%.

5. catalyst as claimed in claim 1, it is characterised in that a kind of catalysis oxidation VOCs catalyst, including carrier and Active component, the carrier are red schorl phase titanium dioxide, and it is by modification, and the modification component used of modifying is Al₂O₃Or La₂O₃, active component is the oxide of ruthenium, is counted using the quality of catalyst as 100wt.%, and the modification component accounts for the matter of catalyst Amount percentage is 5wt.%, and the oxide of active component ruthenium, in terms of the quality of ruthenium, the mass percent for accounting for catalyst is 1wt.%.

6. a kind of preparation method of the catalyst of catalysis oxidation VOCs as described in one of claim 1-5, methods described for etc. Volume impregnation method, comprises the following steps：

(1) red schorl phase titanium dioxide is mixed with the precursor water solution of aluminium or lanthanum, stands after stirring, then done Dry and roasting, the carrier after being modified；

(2) carrier after the modification for obtaining step (1) is added in the precursor water solution of ruthenium, is stood after stirring, so After be dried and be calcined, obtain catalysis oxidation VOCs catalyst.

7. method as claimed in claim 6, it is characterised in that the presoma of aluminium is aluminum nitrate.

8. method as claimed in claim 6, it is characterised in that the presoma of lanthanum is lanthanum nitrate.

9. method as claimed in claim 6, it is characterised in that time of repose is 2~24h in step (1).

10. method as claimed in claim 6, it is characterised in that time of repose is 12h in step (1).

11. method as claimed in claim 6, it is characterised in that drying time is 2~24h in step (1).

12. method as claimed in claim 6, it is characterised in that drying time is 6h in step (1).

13. method as claimed in claim 6, it is characterised in that sintering temperature is 400~600 DEG C in step (1).

14. method as claimed in claim 6, it is characterised in that sintering temperature is 500 DEG C in step (1).

15. method as claimed in claim 6, it is characterised in that roasting time is 2~24h in step (1).

16. method as claimed in claim 6, it is characterised in that roasting time is 6h in step (1).

17. method as claimed in claim 6, it is characterised in that the presoma of step (2) described ruthenium is RuCl₃Or/and Ru (NO)(NO₃)₂。

18. method as claimed in claim 6, it is characterised in that time of repose is 2~24h in step (2).

19. method as claimed in claim 6, it is characterised in that time of repose is 12h in step (2).

20. method as claimed in claim 6, it is characterised in that drying time is 2~24h in step (2).

21. method as claimed in claim 6, it is characterised in that drying time is 6h in step (2).

22. method as claimed in claim 6, it is characterised in that the temperature of step (2) roasting is 200~500 DEG C.

23. method as claimed in claim 6, it is characterised in that the temperature of step (2) roasting is 350 DEG C.

24. method as claimed in claim 6, it is characterised in that step (2) roasting time is 2~24h.

25. method as claimed in claim 6, it is characterised in that step (2) roasting time is 4h.

26. a kind of purposes of the catalyst of catalysis oxidation VOCs as described in one of claim 1-5, the catalyst is used to urge Change and aoxidize various VOCs.