CN104907069B - A kind of catalyst for room temperature purifying formaldehyde and application thereof - Google Patents
A kind of catalyst for room temperature purifying formaldehyde and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for room temperature purifying formaldehyde, the catalyst includes porous inorganic oxide carrier and the active component being supported on carrier and auxiliary agent, the active component includes transition metal active component, and the transition metal is any one in manganese, iron, ruthenium, iridium, osmium, nickel, copper or zinc or at least two combination.The use condition of the catalyst for room temperature purifying formaldehyde is simple, it is easy to operate, can be effectively used under room temperature condition major pollutants formaldehyde in catalysis oxidation room, the catalyst at ambient temperature just can be with catalysis oxidation formaldehyde as carbon dioxide and water, there is no the accessory substances such as formic acid, carbon monoxide and methyl formate, formaldehyde conversion may be up to 100%.
Description
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of catalyst for room temperature purifying formaldehyde.
Background technology
With the raising of people's material and cultural life, interior decoration has turned into fashion, but room air pollution is also got over
Come more serious.Formaldehyde is one of most typically, pollutant of most serious in indoor environment.The room air of China's national Specification
The concentration limit of middle formaldehyde pollutants is 0.08mg/m3.At present, the exceeded situation of concentration of formaldehyde is very tight in China's indoor environment
Weight, the sampling Detection investigation according to national Center for Disease Control finds that the new finishing residential building formaldehyde of China more than 60% is dense
Degree is exceeded, gives people healthy causing and greatly endangers.With the raising of environmental consciousness, people are healed to Formaldehyde Pollution of Indoor Air
Hair concern, the complaint case for causing because indoor formaldehyde concentration is exceeded in recent years is also to appear in the newspapers repeatly.Therefore, purifying formaldehyde skill is studied
Art, effectively eliminating Formaldehyde Pollution of Indoor Air has turned into the urgent task for improving people's living environment.
Existing purifying indoor formaldehyde technology is based on adsorption technology, photocatalysis technology.Adsorption technology mainly using activated carbon,
The high-ratio surface material such as molecular sieve carrys out formaldehyde adsorption, but due to sorbing material limited sorption capacity, needs regular regeneration or replacing, together
When be also easy to produce secondary pollution.Photocatalysis technology mainly utilizes nano-TiO2Carry out decomposing formaldehyde as photochemical catalyst, existing needs purple
The problems such as outer excitation source, catalyst easy in inactivation low to visible light utilization ratio.Non- photochemical catalytic oxidation purifying indoor formaldehyde due to
Light and other energy inputs are not needed, just energy complete catalysts oxidation formaldehyde generates water and carbon dioxide final product at room temperature,
The technology has obtained wide popularization and application.
CN101380574 discloses a kind of catalyst of complete oxidation of formaldehyde at room temperature, the catalyst by porous without
Machine oxide carrier, noble metal component and the part of adjuvant component three composition.Porous inorganic oxide carrier is ceria, two
Zirconium oxide, titanium dioxide, alundum (Al2O3), tin ash, silica, lanthanum sesquioxide, magnesia, zinc oxide therein one
Plant or more than one mixtures or its composite oxides, zeolite, sepiolite, porous Carbon Materials, catalyst noble metal component is
At least one of platinum, rhodium, palladium, gold, silver, adjuvant component are at least one of alkali metal lithium, sodium, potassium, rubidium, caesium.The invention is urged
Load capacity of the noble metal component used in agent based on the conversion of metal element wt is 0.1-10%, preferably 0.3-2%；Help
Load capacity of the agent component based on the conversion of metal element wt is 0.2-30%, preferably 1-10%, when the load capacity of adjuvant component
During less than 0.2% or higher than 30%, the active significant reduction of catalyst room temperature catalytic oxidation formaldehyde.
CN1795970A provides a kind of high activated catalyst for complete oxidation low concentration formaldehyde under room temperature condition.
The catalyst is raw material using metal oxide and very small amount of noble metal simple and easy to get, and preparation method is simple.The catalysis
Agent is main body by metal oxide, and carried noble metal component is constituted on an metal oxide.Aforementioned metal oxides component can be with
It is at least one of following metal oxide group, foregoing noble metal component can be at least one of following noble metal group.
Metal oxide：Ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), lanthanum sesquioxide, magnesia, zinc oxide, oxygen
Change calcium, cupric oxide；Noble metal group:Platinum, gold, rhodium, palladium, silver.The catalyst of the invention, by common metal oxides and a small amount of your gold
Category composition, can be efficiently applied to the catalysis oxidation of formaldehyde under room temperature condition.The catalysis activity of the catalyst of the invention is high, when continuing
Between it is long, the conversion ratio of formaldehyde may be up to 100% at ambient temperature, and product is carbon dioxide and water.
CN102941111A discloses a kind of catalyst of the metal carrier load for room temperature purifying formaldehyde, the catalysis
Agent is by metallic carrier, the porous inorganic material being carried on metallic carrier, the noble metal active being carried on porous inorganic material
Component and auxiliary agent are constituted, and the metallic carrier is Aludirome, and the noble metal is selected from any in platinum, rhodium, palladium, gold or silver
It is a kind of or at least two mixture, the auxiliary agent be alkali metal simple substance, alkali metal compound, alkaline-earth metal simple substance or alkaline earth
In metallic compound any one or at least two mixture.
But, the catalyst of above-mentioned prior art it is expensive, anti humility performance is poor, and stability is poor.
The content of the invention
For the problem of prior art, it is an object of the invention to one of a kind of catalysis for room temperature purifying formaldehyde is provided
Agent, the catalyst keep catalytic efficiency on the premise of, with excellent anti humility performance and stability.
In order to achieve the above object, present invention employs following technical scheme：
A kind of catalyst for room temperature purifying formaldehyde, the catalyst includes carrier, active component and auxiliary agent, described
Carrier be porous inorganic oxide carrier, the active component include transition metal active component, the transition metal be manganese,
In iron, ruthenium, iridium, osmium, nickel, copper or zinc any one or at least two combination.
Preferably, the specific surface area of the porous inorganic oxide carrier is 10~1000m2/ g, such as 20m2/g、50m2/
g、100m2/g、200m2/g、300m2/g、400m2/g、500m2/g、600m2/g、700m2/g、800m2/ g or 900m2/ g, preferably
It is 50~400m2/ g, more preferably 60-180m2/g.Select the specific surface area of the preferably porous inorganic oxide carrier
On the premise of there can be excellent catalysis activity it is ensured, the stability of catalyst is significantly improved.
Preferably, the particle diameter of the porous inorganic oxide carrier be 2-200nm, such as 10nm, 20nm, 40nm, 60nm,
80nm, 100nm, 120nm, 140nm, 160nm or 180nm, preferably 10-100nm, more preferably 20-60nm.Selection should
Preferably particle diameter, can significantly improve the anti humility performance and stability of catalyst.
Preferably, the porous inorganic oxide carrier be ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3),
Any one in tin ash, silica, lanthanum sesquioxide, manganese oxide, iron oxide, calcium oxide, magnesia or zinc oxide
Or at least two mixture or at least two compound, preferably in titanium dioxide, alundum (Al2O3) or silica appoint
Meaning it is a kind of or at least two mixtures.
The mixture is to refer to, the material obtained after each material physical mixed.
The compound is to refer to many metal component oxides prepared by chemical method.
Preferably, the porous inorganic oxide can also be zeolite, sepiolite or porous Carbon Materials.
Preferably, transition metal active component is the metal or the oxide or the inorganic salts of the metal of the metal.
Preferably, the transition metal be manganese, iron, ruthenium or iridium in any one or at least two combination, preferably
Combination, the combination of iron ruthenium or the combination of iron iridium of manganese iridium.Select the preferably transition metal to combine, can be urged catalyst is ensured
On the premise of changing activity, the anti humility performance and stability of catalyst are significantly improved.
Counted with the weight of catalyst as 100%, transition metal is manganese, iron, nickel, copper or zinc, transition metal active component is pressed
Transition metal weight meter, the percentage by weight of transition metal active component is 0.1~50%, such as 0.5%, 1.2%,
1.8%th, 2.4%, 3.2%, 3.8%, 4.5%, 6.1%, 6.9%, 7.2%, 7.8%, 8.4%, 9.2%, 9.6%,
10.5%th, 12.3%, 14.6%, 15.8%, 17.9%, 20.6%, 24.3%, 26.8%, 30.1%, 32.6%, 35.7%,
39.4%th, 41.5%, 43.8%, 46.9%, 48.7% or 49.6%, preferably 10~30%, further preferred 12~25%, then
Further preferred 15~20%.
Counted with the weight of catalyst as 100%, transition metal is ruthenium, iridium or osmium, and transition metal active component is by transition gold
Category element wt meter, the percentage by weight of transition metal active component is 0.1~10%, such as 0.5%, 1.2%, 1.8%,
2.4%th, 3.2%, 3.8%, 4.5%, 6.1%, 6.9%, 7.2%, 7.8%, 8.4%, 9.2%, 9.6%, further preferably
0.2~8%, still further preferably 0.3~3%.
Preferably, the transition metal is the combination of manganese iridium, and the mol ratio of the manganese and iridium is 0.01~0.09, for example
0.02nd, 0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02~0.04, counted with the weight of catalyst as 100%, mistake
Metal active constituent is crossed based on transition metal weight, the percentage by weight of transition metal active component is 0.1~10%, example
Such as 0.5%, 1.2%, 1.8%, 2.4%, 3.2%, 3.8%, 4.5%, 6.1%, 6.9%, 7.2%, 7.8%, 8.4%,
9.2%th, 9.6%.
Preferably, the transition metal is the combination of iron ruthenium, and the mol ratio of the iron and ruthenium is 0.01~0.09, for example
0.02nd, 0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02~0.03, counted with the weight of catalyst as 100%, mistake
Metal active constituent is crossed based on transition metal weight, the percentage by weight of transition metal active component is 0.1~10%, example
Such as 0.5%, 1.2%, 1.8%, 2.4%, 3.2%, 3.8%, 4.5%, 6.1%, 6.9%, 7.2%, 7.8%, 8.4%,
9.2%th, 9.6%.
Preferably, the transition metal is the combination of iron iridium, and the mol ratio of the iron and iridium is 0.01~0.09, for example
0.02nd, 0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02~0.03, counted with the weight of catalyst as 100%, mistake
Metal active constituent is crossed based on transition metal weight, the percentage by weight of transition metal active component is 0.1~10%, example
Such as 0.5%, 1.2%, 1.8%, 2.4%, 3.2%, 3.8%, 4.5%, 6.1%, 6.9%, 7.2%, 7.8%, 8.4%,
9.2%th, 9.6%.
Preferably, thus auxiliary agent be the oxide in alkali metal or alkaline-earth metal or any one in hydroxide or
At least two combination, is counted with the weight of catalyst as 100%, and the percentage by weight of adjuvant component is 0.1~40%, further
It is preferred that 0.5~20%, still further preferably 2~10%.
The preparation method of the catalyst of the metal carrier load for room temperature purifying formaldehyde is prior art, affiliated neck
The technical staff in domain can be according to disclosed in prior art the preparation method of catalyst prepare above-mentioned catalyst.
The preparation method of the exemplary catalyst for room temperature purifying formaldehyde comprises the following steps：
Infusion process：By porous inorganic oxide carrier impregnation in transition metal and the soluble compounds aqueous solution of promoter metal
In, stir 1~5 hour, in 80~120 DEG C of dryings, under air or nitrogen or hydrogen atmosphere, in 200~700 DEG C of roastings of Muffle furnace
Burn 1~8 hour.
Catalyst of the invention, can such as be supported on honeycomb ceramic body or gold according to various structures are made the need for difference
On the wall surface of the mesh structure that category is made, open-celled foams are also used as the structural carrier of catalyst.Alternatively, it is also possible to
Catalyst is made into spherical or tabular to use.The detailed process above-mentioned catalyst being supported on honeycomb ceramic carrier is：First
The mixing such as the catalyst and deionized water that will prepare is made into the mixture of certain solid concentration, and then above-mentioned mixed liquor is entered
Row ball milling, forms the slurries with certain solid content, viscosity, proportion, catalyst granules and pH, is then coated, dries
And after roasting, obtain integral catalyzer.
The second object of the present invention is to provide a kind of purposes of the catalyst for being used for room temperature purifying formaldehyde as described above,
It is used for room temperature purifying formaldehyde.
Preferably, the method that catalyst is used for room temperature purifying formaldehyde is comprised the following steps：
Fine catalyst shaping is prepared into catalytic purification formaldehyde module first, then assembling forms catalytic purification formaldehyde
Component, is then put it into air purifier or other air cleaning units, and formaldehyde will be contained under the perturbation action of air
Dusty gas by said apparatus, and with catalytic purification component touch, so as to realize the purification of formaldehyde at room temperature.
Compared with prior art, the present invention has the advantages that：
The high catalytic efficiency of the catalyst for room temperature purifying formaldehyde, is assembled in the energy consumption caused after cleaning equipment
It is low, and low cost.
The use condition of the catalyst for room temperature purifying formaldehyde is simple, easy to operate, can be effectively used for room temperature bar
Major pollutants formaldehyde in catalysis oxidation room under part, the catalyst at ambient temperature just can be with catalysis oxidation formaldehyde as titanium dioxide
Carbon and water, do not have the accessory substances such as formic acid, carbon monoxide and methyl formate, and formaldehyde conversion may be up to 100%.
At room temperature, under the conditions of normal wet (humidity 50%), formaldehyde conversion can reach 100%, height to the catalyst
Under humidity in the environment of (>=90%), formaldehyde catalytic conversion is very high, and it can still keep more than 90% conversion ratio.And
And, the catalyst has stability high, at room temperature and often it is wet under the conditions of, in 500h, formaldehyde conversion can reach
95% and more than, humidity be >=90% in the environment of, in 5000h, formaldehyde conversion can still reach more than 85%.Cause
This, the catalyst has excellent stability and anti humility performance.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, it is of the invention typical but non-limiting
Embodiment is as follows：
Embodiment 1
A kind of catalyst for room temperature purifying formaldehyde, the catalyst is by porous inorganic oxide and is carried on porous
Transition metal active component and auxiliary agent composition on inorganic oxide, the porous inorganic oxide is ceria, and it compares table
Area is 10m2/ g, particle diameter is 30nm, and active component is manganese-iridium composite oxide, and the mol ratio of the manganese and iridium is 0.03, with
The weight of catalyst be 100% meter, transition metal active component based on transition metal weight, transition metal active component
Percentage by weight is 5%, and the auxiliary agent is barium monoxide, and auxiliary agent content is 8%.
Embodiment 2
Remaining is same as Example 1, except specific surface area is 1000m2/g。
Embodiment 3
Remaining is same as Example 1, except specific surface area is 60m2/g。
Embodiment 4
Remaining is same as Example 1, except specific surface area is 180m2/g。
The catalyst of 60mg embodiments 1~4 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, activity rating knot
Fruit is as shown in table 1.
Table 1
The catalyst of 60mg embodiments 1~4 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Embodiment 1 and 2
Catalyst in 500h, formaldehyde conversion maintains more than 90% always, the catalyst of embodiment 3~4 in 500h, formaldehyde
Conversion ratio maintains more than 95% always.
The catalyst of 60mg embodiments 1~4 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, and it is 0.01%, phase to control concentration of formaldehyde
To humidity from 50%-90%, reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, the Activity evaluation such as institute of table 2
Show.
The catalyst activity evaluation result of table 2
The catalyst of 60mg embodiments 1~4 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 90%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Embodiment 1 and 2
Catalyst in 500h, formaldehyde conversion maintains more than 60% always, the catalyst of embodiment 3~4 in 500h, formaldehyde
Conversion ratio maintains more than 90% always.
Above example 1~4 illustrates that porous inorganic oxide carrier has shadow to the catalysis activity and stability of catalyst
Ring, as 60~180m of selection2During/g, the catalysis activity and stability of catalyst are significantly improved.
Embodiment 5
Remaining is same as Example 1, except the particle diameter of ceria is 2nm.
Embodiment 6
Remaining is same as Example 1, except the particle diameter of ceria is 200nm.
Embodiment 7
Remaining is same as Example 1, except the particle diameter of ceria is 20nm.
Embodiment 8
Remaining is same as Example 1, except the particle diameter of ceria is 60nm.
The catalyst of 60mg embodiments 5~8 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, suitable humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, activity rating knot
Fruit is as shown in table 3.
Table 3
The catalyst of 60mg embodiments 5~8 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, suitable humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Embodiment 5 and 6
Catalyst in 500h, formaldehyde conversion maintains more than 90% always, the catalyst of embodiment 7 and 8 in 500h, formaldehyde
Conversion ratio maintains more than 95% always.
The catalyst of 60mg embodiments 5~8 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, and it is 0.01%, phase to control concentration of formaldehyde
To humidity from 50%-90%, reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, the Activity evaluation such as institute of table 4
Show.
The catalyst activity evaluation result of table 4
The catalyst of 60mg embodiments 1~4 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, suitable humidity 90%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Embodiment 5 and 6
Catalyst in 500h, formaldehyde conversion maintains more than 65% always, the catalyst of embodiment 7 and 8 in 500h, formaldehyde
Conversion ratio maintains more than 90% always.
Above example 1 and 5~8 illustrates, the particle diameter of porous inorganic oxide carrier to the catalysis activity of catalyst and
Stability has an impact, and when 20~60nm is selected, significantly improves the catalysis activity and stability of catalyst.
Embodiment 9
Remaining is same as Example 1, except transition metal active component is iron ruthenium composite oxides, the iron and ruthenium mole
Than being 0.03, counted with the weight of catalyst as 100%, transition metal active component is based on transition metal weight, and transition is golden
The percentage by weight for belonging to active component is 5%.
Embodiment 10
Remaining is same as Example 1, except transition metal active component is iron iridium composite oxide, the iron and iridium mole
Than being 0.03, counted with the weight of catalyst as 100%, transition metal active component is based on transition metal weight, and transition is golden
The percentage by weight for belonging to active component is 5%.
Embodiment 11
Remaining is same as Example 1, except active component is nickel.
Embodiment 12
Remaining is same as Example 1, except active component is copper.
Embodiment 13
Remaining is same as Example 1, except active component is zinc.
The catalyst of 60mg embodiments 9~13 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, activity rating knot
Fruit is as shown in table 5.
Table 5
The catalyst of 60mg embodiments 9~13 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.The He of embodiment 9
In 500h, formaldehyde conversion maintains more than 95% to 10 catalyst always, the catalyst of embodiment 11~13 in 500h,
Formaldehyde conversion maintains more than 85% always.
The catalyst of 60mg embodiments 9~13 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, and it is 0.01%, phase to control concentration of formaldehyde
When humidity from 50%-90%, reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, the Activity evaluation such as institute of table 6
Show.
The catalyst activity evaluation result of table 6
The catalyst of 60mg embodiments 9~13 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, suitable humidity 90%, formaldehyde gas is produced with formaldehyde gas generator, is blown into instead by helium
System is answered, it is 0.01% to control concentration of formaldehyde, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.The He of embodiment 9
In 500h, formaldehyde conversion maintains more than 90% to 10 catalyst always, the catalyst of embodiment 11~13 in 500h,
Formaldehyde conversion maintains more than 60% always.
Comparative example 1
Remaining is same as Example 1, and except active component is noble metal active component, the noble metal is Ag.
Comparative example 2
Remaining is same as Example 1, except the specific surface area of porous inorganic oxide carrier is 5m2/g。
Comparative example 3
Remaining is same as Example 1, except the specific surface area of porous inorganic oxide carrier is 1100m2/g。
Comparative example 4
Remaining is same as Example 1, except the particle diameter of porous inorganic oxide is 1nm.
Comparative example 5
Remaining is same as Example 1, except the particle diameter of porous inorganic oxide is 220nm.
Comparative example 6
Remaining is same as Example 1, and the mol ratio of demanganization and iridium is 0.005.
Comparative example 7
Remaining is same as Example 1, and the mol ratio of demanganization and iridium is 0.10.
Comparative example 8
Remaining is same as Example 9, except the mol ratio of iron and ruthenium is 0.005.
Comparative example 9
Remaining is same as Example 9, except the mol ratio of iron and ruthenium is 0.10.
Comparative example 10
Remaining is same as in Example 10, except the mol ratio of iron and iridium is 0.005.
Comparative example 11
Remaining is same as in Example 10, except the mol ratio of iron and iridium is 0.10.
The catalyst of 60mg comparative examples 1~11 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, activity rating knot
Fruit is as shown in table 7 and table 8.
Table 7
Table 8
The catalyst of 60mg comparative examples 1~11 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 50%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Comparative example 1~
In 500 hours, formaldehyde conversion maintains more than 75% to 11 catalyst always.
The catalyst of 60mg comparative examples 1~11 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, and it is 0.01%, phase to control concentration of formaldehyde
To humidity from 50%-90%, reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature, the Activity evaluation such as institute of table 9
Show.
The catalyst activity evaluation result of table 9
The catalyst of 60mg comparative examples 1~11 is taken respectively, is positioned in tubular fixed-bed reactor and is tested, experiment condition
It is as follows：Oxygen 20%, helium 80%, formaldehyde gas is produced with formaldehyde gas generator, and reaction system is blown into by helium, controls first
Aldehyde concentration is 0.01%, relative humidity 90%, and reaction velocity (GHSV) is 50000h-1, reaction temperature is room temperature.Comparative example 1~
In 500 hours, formaldehyde conversion maintains more than 50% to 11 catalyst always.
Applicant states that the present invention illustrates the detailed composition of catalyst of the present invention, but this by above-described embodiment
Invention is not limited to above-mentioned detailed composition, that is, do not mean that the present invention has to rely on above-mentioned detailed composition and could implement.It is affiliated
Those skilled in the art it will be clearly understood that any improvement in the present invention, equivalence replacement to each raw material of product of the present invention and
The addition of auxiliary element, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (19)
1. a kind of catalyst for room temperature purifying formaldehyde, the catalyst includes carrier, active component and auxiliary agent, the load
Body is porous inorganic oxide carrier, and the active component includes transition metal active component, and the transition metal is manganese iridium
The mol ratio of combination, the manganese and iridium is 0.01~0.09, is counted with the weight of catalyst as 100%, transition metal active component
Based on transition metal weight, the percentage by weight of transition metal active component is 0.1~10%；Or,
The transition metal is the combination of iron ruthenium, and the mol ratio of the iron and ruthenium is 0.01~0.09, and the weight with catalyst is
100% meter, based on transition metal weight, the percentage by weight of transition metal active component is transition metal active component
0.1~10%；Or,
The transition metal is the combination of iron iridium, and the mol ratio of the iron and iridium is 0.01~0.09, and the weight with catalyst is
100% meter, based on transition metal weight, the percentage by weight of transition metal active component is transition metal active component
0.1~10%.
2. catalyst as claimed in claim 1, it is characterised in that the specific surface area of the porous inorganic oxide carrier is 10
~1000m2/g。
3. catalyst as claimed in claim 1, it is characterised in that the specific surface area of the porous inorganic oxide carrier is 50
~400m2/g。
4. catalyst as claimed in claim 1, it is characterised in that the specific surface area of the porous inorganic oxide carrier is
60-180m2/g。
5. catalyst as claimed in claim 1 or 2, it is characterised in that the particle diameter of the porous inorganic oxide carrier is 2-
200nm。
6. catalyst as claimed in claim 1 or 2, it is characterised in that the particle diameter of the porous inorganic oxide carrier is 10-
100nm。
7. catalyst as claimed in claim 1 or 2, it is characterised in that the particle diameter of the porous inorganic oxide carrier is 20-
60nm。
8. the catalyst as described in one of claim 1-3, it is characterised in that the porous inorganic oxide carrier is titanium dioxide
Cerium, zirconium dioxide, titanium dioxide, alundum (Al2O3), tin ash, silica, lanthanum sesquioxide, manganese oxide, iron oxide, oxygen
Change in calcium, magnesia or zinc oxide any one or at least two mixture or at least two compound.
9. the catalyst as described in one of claim 1-3, it is characterised in that the porous inorganic oxide carrier is titanium dioxide
In titanium, alundum (Al2O3) or silica any one or at least two mixture.
10. the catalyst as described in one of claim 1-3, it is characterised in that the porous inorganic oxide is zeolite, Hai Pao
Stone or porous Carbon Materials.
11. catalyst as described in one of claim 1-3, it is characterised in that transition metal active component is the metal or is somebody's turn to do
The inorganic salts of the oxide of metal or the metal.
12. catalyst as described in one of claim 1-3, it is characterised in that the mol ratio of the manganese and iridium be 0.02~
0.04。
13. catalyst as described in one of claim 1-3, it is characterised in that the mol ratio of the iron and ruthenium be 0.02~
0.03。
14. catalyst as described in one of claim 1-3, it is characterised in that the mol ratio of the iron and iridium be 0.02~
0.03。
15. catalyst as described in one of claim 1-3, it is characterised in that so adjuvant component is alkali metal or alkaline earth gold
In oxide or hydroxide in category any one or at least two combination, counted with the weight of catalyst as 100%,
The percentage by weight of adjuvant component is 0.1~40%.
16. catalyst as claimed in claim 15, it is characterised in that the percentage by weight of adjuvant component is 0.5~20%.
17. catalyst as claimed in claim 16, it is characterised in that the percentage by weight of adjuvant component is 2~10%.
The purposes of 18. a kind of catalyst as described in one of claim 1-17, it is characterised in that the catalyst is used for room temperature
Purifying formaldehyde.
19. purposes as claimed in claim 18, it is characterised in that include such as the method that catalyst is used for room temperature purifying formaldehyde
Lower step：
Fine catalyst shaping is prepared into catalytic purification formaldehyde module first, then assembling forms catalytic purification formaldehyde group
Part, is then put it into air purifier or other air cleaning units, and formaldehyde will be contained under the perturbation action of air
Dusty gas by said apparatus, and with catalytic purification component touch, so as to realize the purification of formaldehyde at room temperature.
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