CN104907069A - Catalyst for room temperature formaldehyde purification, and use thereof - Google Patents
Catalyst for room temperature formaldehyde purification, and use thereof Download PDFInfo
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- CN104907069A CN104907069A CN201510192626.1A CN201510192626A CN104907069A CN 104907069 A CN104907069 A CN 104907069A CN 201510192626 A CN201510192626 A CN 201510192626A CN 104907069 A CN104907069 A CN 104907069A
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Abstract
The invention relates to a catalyst for room temperature formaldehyde purification. The catalyst comprises a porous inorganic oxide carrier, and an active component and an assistant which are loaded on the carrier, the active component comprises a transition metal active component, and the transition metal is anyone of or a combination containing at least two of manganese, iron, ruthenium, iridium, osmium, nickel, copper and zinc. The catalyst for room temperature formaldehyde purification can be used under simple conditions, is convenient to operate, can effectively catalyze the main indoor pollutant formaldehyde under room temperature conditions, can catalyze oxidation of formaldehyde under room temperature conditions to form carbon dioxide water without formic acid, carbon monoxide, methyl formate or other byproducts, and allows he formaldehyde conversion rate to reach 100%.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of catalyst for room temperature purifying formaldehyde.
Background technology
Along with the raising of people's material and cultural life, interior decoration becomes fashion, but room air pollution is also more and more serious.Formaldehyde is one of pollutant typical, the most serious in indoor environment.The concentration limit of the formaldehyde in indoor air pollutant of China's national Specification is 0.08mg/m
3.At present, the situation that in China's indoor environment, concentration of formaldehyde exceeds standard is very serious, and the sampling Detection investigation according to national Center for Disease Control finds, the new finishing residential building concentration of formaldehyde of China more than 60% exceeds standard, and causes great harm to people are healthy.Along with the raising of environmental consciousness, people more pay close attention to Formaldehyde Pollution of Indoor Air, in recent years because the indoor formaldehyde concentration complaint case caused that exceeds standard also is appear in the newspapers repeatly.Therefore, research purifying formaldehyde technology, effectively eliminating Formaldehyde Pollution of Indoor Air has become the urgent task improving people's living environment.
Existing purifying indoor formaldehyde technology is based on adsorption technology, photocatalysis technology.Adsorption technology mainly adopts the high-ratio surface such as active carbon, molecular sieve material to carry out formaldehyde adsorption, but due to sorbing material limited sorption capacity, needs regular regeneration or replacing, easily produces secondary pollution simultaneously.Photocatalysis technology mainly utilizes nano-TiO
2carry out decomposing formaldehyde as photochemical catalyst, there is problems such as needing burst of ultraviolel light source, catalyst easy in inactivation low to visible ray utilization ratio.Non-photochemical catalytic oxidation purifying indoor formaldehyde is not owing to needing light and the input of other energy, and at room temperature just can generate water and carbon dioxide end product by complete catalysts oxidation formaldehyde, this technology obtains wide popularization and application.
CN101380574 discloses a kind of catalyst of complete oxidation of formaldehyde at room temperature, this catalyst by porous inorganic oxide carrier, noble metal component and adjuvant component three part form.Porous inorganic oxide carrier is ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), tin ash, silica, lanthanum sesquioxide, magnesia, zinc oxide one or more mixtures wherein or its composite oxides, zeolite, sepiolite, porous Carbon Materials, catalyst noble metal component is at least one in platinum, rhodium, palladium, gold, silver, and adjuvant component is at least one in alkali metal lithium, sodium, potassium, rubidium, caesium.The load capacity that the noble metal component used in the catalyst of this invention converts by metal element wt is 0.1-10%, is preferably 0.3-2%; The load capacity that adjuvant component converts by metal element wt is 0.2-30%, be preferably 1-10%, when adjuvant component load capacity lower than 0.2% or higher than 30% time, the activity of catalyst room temperature catalyze oxidation of formaldehyde shows and reduces.
CN1795970A provides a kind of high activated catalyst for complete oxidation low concentration formaldehyde under room temperature condition.This catalyst uses metal oxide simple and easy to get and very small amount of noble metal to be raw material, and preparation method is simple.This catalyst is main body by metal oxide, and carried noble metal component is formed on an metal oxide.Aforementioned metal oxides component can be at least one in following metal oxide group, and aforementioned noble metal component can be at least one in following noble metal group.Metal oxide: ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), lanthanum sesquioxide, magnesia, zinc oxide, calcium oxide, cupric oxide; Noble metal group: platinum, gold, rhodium, palladium, silver.The catalyst of this invention, is made up of common metal oxides and a small amount of noble metal, effectively can be applied to the catalytic oxidation of formaldehyde under room temperature condition.The catalytic activity of the catalyst of this invention is high, and the duration is long, and the conversion ratio of formaldehyde can 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, described catalyst is by metallic carrier, be carried on the porous inorganic material on metallic carrier, be carried on the noble metal active component on porous inorganic material and auxiliary agent composition, described metallic carrier is Aludirome, described noble metal is selected from platinum, rhodium, palladium, the mixture of any one or at least two kinds in gold or silver, described auxiliary agent is alkali metal simple substance, alkali metal compound, the mixture of any one or at least two kinds in alkaline-earth metal simple substance or alkaline earth metal compound.
But, the catalyst of above-mentioned prior art expensive, anti humility performance is poor, and poor stability.
Summary of the invention
For the problem of prior art, one of to the object of the invention is to provide a kind of catalyst for room temperature purifying formaldehyde, described catalyst, under the prerequisite keeping catalytic efficiency, has 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, described catalyst comprises carrier, active component and auxiliary agent, described carrier is porous inorganic oxide carrier, described active component comprises transition metal active component, and described transition metal is the combination of any one or at least two kinds in manganese, iron, ruthenium, iridium, osmium, nickel, copper or zinc.
Preferably, the specific area of described porous inorganic oxide carrier is 10 ~ 1000m
2/ g, such as 20m
2/ g, 50m
2/ g, 100m
2/ g, 200m
2/ g, 300m
2/ g, 400m
2/ g, 500m
2/ g, 600m
2/ g, 700m
2/ g, 800m
2/ g or 900m
2/ g, is preferably 50 ~ 400m
2/ g, more preferably 60-180m
2/ g.Select the specific area of this preferably porous inorganic oxide carrier under ensureing that it has the prerequisite of excellent catalytic activity, the stability of catalyst can be significantly improved.
Preferably, the particle diameter of described porous inorganic oxide carrier is 2-200nm, such as 10nm, 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm or 180nm, is preferably 10-100nm, more preferably 20-60nm.Select this preferably particle diameter, anti humility performance and the stability of catalyst can be significantly improved.
Preferably, described porous inorganic oxide carrier is any one or the mixture of at least two kinds in ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), tin ash, silica, lanthanum sesquioxide, manganese oxide, iron oxide, calcium oxide, magnesia or zinc oxide or the compound of at least two kinds, the mixture of any one or at least two kinds in preferred titanium dioxide, alundum (Al2O3) or silica.
Namely described mixture refers to, the material obtained after each material physical mixed.
Namely described compound refers to the many metal components oxide prepared by chemical method.
Preferably, described porous inorganic oxide can also be zeolite, sepiolite or porous Carbon Materials.
Preferably, transition metal active component is the oxide of this metal or this metal or the inorganic salts of this metal.
Preferably, described transition metal is the combination of any one or at least two kinds in manganese, iron, ruthenium or iridium, the combination of the combination of preferred manganese iridium, the combination of iron ruthenium or iron iridium.Select this preferably transition metal combination, under the prerequisite ensureing catalyst activity, anti humility performance and the stability of catalyst can be significantly improved.
In the weight of catalyst for 100%, transition metal is manganese, iron, nickel, copper or zinc, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 50%, 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%, 9.6%, 10.5%, 12.3%, 14.6%, 15.8%, 17.9%, 20.6%, 24.3%, 26.8%, 30.1%, 32.6%, 35.7%, 39.4%, 41.5%, 43.8%, 46.9%, 48.7% or 49.6%, preferably 10 ~ 30%, further preferably 12 ~ 25%, again further preferably 15 ~ 20%.
In the weight of catalyst for 100%, transition metal is ruthenium, iridium or osmium, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 10%, 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%, 9.6%, further preferably 0.2 ~ 8%, more further preferably 0.3 ~ 3%.
Preferably, described transition metal is the combination of manganese iridium, the mol ratio of described manganese and iridium is 0.01 ~ 0.09, such as 0.02,0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02 ~ 0.04, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 10%, 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%, 9.6%.
Preferably, described transition metal is the combination of iron ruthenium, the mol ratio of described iron and ruthenium is 0.01 ~ 0.09, such as 0.02,0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02 ~ 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 10%, 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%, 9.6%.
Preferably, described transition metal is the combination of iron iridium, the mol ratio of described iron and iridium is 0.01 ~ 0.09, such as 0.02,0.03,0.04,0.05,0.06,0.07 or 0.08, preferably 0.02 ~ 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 10%, 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%, 9.6%.
Preferably, so auxiliary agent is the combination of oxide in alkali metal or alkaline-earth metal or any one or at least two kinds in hydroxide, in the weight of catalyst for 100%, the percentage by weight of adjuvant component is 0.1 ~ 40%, further preferably 0.5 ~ 20%, more further preferably 2 ~ 10%.
The preparation method of the catalyst of the described metal carrier load for room temperature purifying formaldehyde is prior art, and those skilled in the art can prepare above-mentioned catalyst according to the preparation method of catalyst disclosed in prior art.
The preparation method of the exemplary described catalyst for room temperature purifying formaldehyde comprises the steps:
Infusion process: by porous inorganic oxide carrier impregnation in the soluble compounds aqueous solution of transition metal and promoter metal, stir 1 ~ 5 hour, 80 ~ 120 DEG C of dryings, under air or nitrogen or hydrogen atmosphere, in Muffle furnace 200 ~ 700 DEG C of roastings 1 ~ 8 hour.
Catalyst of the present invention, can make various structure according to different needs, and if load is on the wall surface of honeycomb ceramic body or metal mesh structure, open-celled foams also can be used as the structural carrier of catalyst.In addition, also catalyst can be made spherical or tabular use.By the detailed process of above-mentioned catalyst cupport on honeycomb ceramic carrier be: the mixture first mixing such as the catalyst prepared and deionized water being made into certain solid concentration, then ball milling is carried out to above-mentioned mixed liquor, form the slurries with certain solid content, viscosity, proportion, catalyst granules and pH, then carry out applying, after dry and roasting, obtain integral catalyzer.
Two of object of the present invention is to provide a kind of as above for the purposes of the catalyst of room temperature purifying formaldehyde, and it is for room temperature purifying formaldehyde.
Preferably, method catalyst being used for room temperature purifying formaldehyde comprises the steps:
First catalytic purification formaldehyde module is prepared by shaping for fine catalyst, then assembling forms catalytic purification formaldehyde assembly, then put it in air purifier or other air cleaning units, under the perturbation action of air, the dusty gas containing formaldehyde is passed through said apparatus, and and catalytic purification component touch, thus the purification of formaldehyde under realizing room temperature.
Compared with prior art, the present invention has following beneficial effect:
The catalytic efficiency of the described catalyst for room temperature purifying formaldehyde is high, and the energy consumption caused after being assembled in cleaning equipment is low, and cost is low.
The service condition of the described catalyst for room temperature purifying formaldehyde is simple, easy to operate, the indoor major pollutants formaldehyde of catalytic oxidation under room temperature condition can be effective to, this catalyst can catalyze oxidation of formaldehyde be just carbon dioxide and water at ambient temperature, do not have the accessory substances such as formic acid, carbon monoxide and methyl formate, formaldehyde conversion can up to 100%.
Described catalyst at room temperature, under normal wet (humidity 50%) condition, formaldehyde conversion can reach 100%, under high humility (>=90%) environment under, formaldehyde catalytic conversion is very high, and it is at the conversion ratio that still can to keep more than 90%.And described catalyst has high stability, at room temperature and under normal wet condition, in 500h, formaldehyde conversion can reach 95% and more than, be under the environment of >=90% in humidity, in 5000h, formaldehyde conversion still can reach more than 85%.Therefore, described catalyst has excellent stability and anti humility performance.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
For a catalyst for room temperature purifying formaldehyde, described catalyst is made up of porous inorganic oxide and the transition metal active component be carried on porous inorganic oxide and auxiliary agent, and described porous inorganic oxide is ceria, and its specific area is 10m
2/ g, particle diameter is 30nm, active component is manganese-iridium composite oxide, the mol ratio of described manganese and iridium is 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 5%, described auxiliary agent is barium monoxide, and auxiliary agent content is 8%.
Embodiment 2
All the other are identical with embodiment 1, except specific area is 1000m
2/ g.
Embodiment 3
All the other are identical with embodiment 1, except specific area is 60m
2/ g.
Embodiment 4
All the other are identical with embodiment 1, except specific area is 180m
2/ g.
Get 60mg embodiment 1 ~ 4 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 1.
Table 1
Get 60mg embodiment 1 ~ 4 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 1 and 2 is in 500h, and formaldehyde conversion maintains more than 90% always, and the catalyst of embodiment 3 ~ 4 is in 500h, and formaldehyde conversion maintains more than 95% always.
Get 60mg embodiment 1 ~ 4 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: formaldehyde gas formaldehyde gas generator produces, reaction system is blown into by helium, controlling concentration of formaldehyde is 0.01%, relative humidity is from 50%-90%, and reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 2.
Table 2 catalyst activity evaluation result
Get 60mg embodiment 1 ~ 4 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 90%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 1 and 2 is in 500h, and formaldehyde conversion maintains more than 60% always, and the catalyst of embodiment 3 ~ 4 is in 500h, and formaldehyde conversion maintains more than 90% always.
Above embodiment 1 ~ 4 illustrates, porous inorganic oxide carrier has impact to the catalytic activity of catalyst and stability, as selection 60 ~ 180m
2during/g, significantly improve catalytic activity and the stability of catalyst.
Embodiment 5
All the other are identical with embodiment 1, and the particle diameter except ceria is 2nm.
Embodiment 6
All the other are identical with embodiment 1, and the particle diameter except ceria is 200nm.
Embodiment 7
All the other are identical with embodiment 1, and the particle diameter except ceria is 20nm.
Embodiment 8
All the other are identical with embodiment 1, and the particle diameter except ceria is 60nm.
Get 60mg embodiment 5 ~ 8 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, suitable humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 3.
Table 3
Get 60mg embodiment 5 ~ 8 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, suitable humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 5 and 6 is in 500h, and formaldehyde conversion maintains more than 90% always, and the catalyst of embodiment 7 and 8 is in 500h, and formaldehyde conversion maintains more than 95% always.
Get 60mg embodiment 5 ~ 8 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: formaldehyde gas formaldehyde gas generator produces, reaction system is blown into by helium, controlling concentration of formaldehyde is 0.01%, relative humidity is from 50%-90%, and reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 4.
Table 4 catalyst activity evaluation result
Get 60mg embodiment 1 ~ 4 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, suitable humidity 90%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 5 and 6 is in 500h, and formaldehyde conversion maintains more than 65% always, and the catalyst of embodiment 7 and 8 is in 500h, and formaldehyde conversion maintains more than 90% always.
Above embodiment 1 and 5 ~ 8 illustrates, the particle diameter of porous inorganic oxide carrier has impact to the catalytic activity of catalyst and stability, as selection 20 ~ 60nm, significantly improves catalytic activity and the stability of catalyst.
Embodiment 9
All the other are identical with embodiment 1, except transition metal active component is iron ruthenium composite oxides, the mol ratio of described iron and ruthenium is 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 5%.
Embodiment 10
All the other are identical with embodiment 1, except transition metal active component is iron iridium composite oxide, the mol ratio of described iron and iridium is 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 5%.
Embodiment 11
All the other are identical with embodiment 1, except active component is nickel.
Embodiment 12
All the other are identical with embodiment 1, except active component is copper.
Embodiment 13
All the other are identical with embodiment 1, except active component is zinc.
Get 60mg embodiment 9 ~ 13 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 5.
Table 5
Get 60mg embodiment 9 ~ 13 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 9 and 10 is in 500h, and formaldehyde conversion maintains more than 95% always, and the catalyst of embodiment 11 ~ 13 is in 500h, and formaldehyde conversion maintains more than 85% always.
Get 60mg embodiment 9 ~ 13 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: formaldehyde gas formaldehyde gas generator produces, reaction system is blown into by helium, controlling concentration of formaldehyde is 0.01%, suitable humidity is from 50%-90%, and reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 6.
Table 6 catalyst activity evaluation result
Get 60mg embodiment 9 ~ 13 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, suitable humidity 90%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, controlling concentration of formaldehyde is 0.01%, and reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of embodiment 9 and 10 is in 500h, and formaldehyde conversion maintains more than 90% always, and the catalyst of embodiment 11 ~ 13 is in 500h, and formaldehyde conversion maintains more than 60% always.
Comparative example 1
All the other are identical with embodiment 1, and except active component is noble metal active component, described noble metal is Ag.
Comparative example 2
All the other are identical with embodiment 1, and the specific area except porous inorganic oxide carrier is 5m
2/ g.
Comparative example 3
All the other are identical with embodiment 1, and the specific area except porous inorganic oxide carrier is 1100m
2/ g.
Comparative example 4
All the other are identical with embodiment 1, and the particle diameter except porous inorganic oxide is 1nm.
Comparative example 5
All the other are identical with embodiment 1, and the particle diameter except porous inorganic oxide is 220nm.
Comparative example 6
All the other are identical with embodiment 1, and the mol ratio of demanganization and iridium is 0.005.
Comparative example 7
All the other are identical with embodiment 1, and the mol ratio of demanganization and iridium is 0.10.
Comparative example 8
All the other are identical with embodiment 9, and the mol ratio of deironing and ruthenium is 0.005.
Comparative example 9
All the other are identical with embodiment 9, and the mol ratio of deironing and ruthenium is 0.10.
Comparative example 10
All the other are identical with embodiment 10, and the mol ratio of deironing and iridium is 0.005.
Comparative example 11
All the other are identical with embodiment 10, and the mol ratio of deironing and iridium is 0.10.
Get 60mg comparative example 1 ~ 11 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 7 and table 8.
Table 7
Table 8
Get 60mg comparative example 1 ~ 11 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 50%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of comparative example 1 ~ 11 is in 500 hours, and formaldehyde conversion maintains more than 75% always.
Get 60mg comparative example 1 ~ 11 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: formaldehyde gas formaldehyde gas generator produces, reaction system is blown into by helium, controlling concentration of formaldehyde is 0.01%, relative humidity is from 50%-90%, and reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature, and Activity evaluation is as shown in table 9.
Table 9 catalyst activity evaluation result
Get 60mg comparative example 1 ~ 11 catalyst respectively, be positioned in tubular fixed-bed reactor and test, experiment condition is as follows: oxygen 20%, helium 80%, formaldehyde gas formaldehyde gas generator produces, and is blown into reaction system by helium, and controlling concentration of formaldehyde is 0.01%, relative humidity 90%, reaction velocity (GHSV) is 50000h
-1, reaction temperature is room temperature.The catalyst of comparative example 1 ~ 11 is in 500 hours, and formaldehyde conversion maintains more than 50% always.
Applicant states, the present invention illustrates the detailed composition of catalyst of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed composition, does not namely mean that the present invention must rely on above-mentioned detailed composition 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 catalyst for room temperature purifying formaldehyde, described catalyst comprises carrier, active component and auxiliary agent, described carrier is porous inorganic oxide carrier, described active component comprises transition metal active component, and described transition metal is the combination of any one or at least two kinds in manganese, iron, ruthenium, iridium, osmium, nickel, copper or zinc.
2. catalyst as claimed in claim 1, it is characterized in that, the specific area of described porous inorganic oxide carrier is 10 ~ 1000m
2/ g, is preferably 50 ~ 400m
2/ g, more preferably 60-180m
2/ g.
3. catalyst as claimed in claim 1 or 2, it is characterized in that, the particle diameter of described porous inorganic oxide carrier is 2-200nm, is preferably 10-100nm, more preferably 20-60nm.
4. the catalyst as described in one of claim 1-3, it is characterized in that, described porous inorganic oxide carrier is any one or the mixture of at least two kinds in ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), tin ash, silica, lanthanum sesquioxide, manganese oxide, iron oxide, calcium oxide, magnesia or zinc oxide or the compound of at least two kinds, and preferred described porous inorganic oxide carrier is the mixture of any one or at least two kinds in titanium dioxide, alundum (Al2O3) or silica.
5. the catalyst as described in one of claim 1-3, is characterized in that, described porous inorganic oxide is also zeolite, sepiolite or porous Carbon Materials.
6. the catalyst as described in one of claim 1-5, is characterized in that, described transition metal is the combination of any one or at least two kinds in manganese, iron, ruthenium or iridium, the combination of the combination of preferred manganese iridium, the combination of iron ruthenium or iron iridium.
7. the catalyst as described in one of claim 1-6, is characterized in that, transition metal active component is the oxide of this metal or this metal or the inorganic salts of this metal;
Preferably, in the weight of catalyst for 100%, transition metal is manganese, iron, nickel, copper or zinc, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 50%, preferably 10 ~ 30%, further preferably 12 ~ 25%, more further preferably 15 ~ 20%.
8. the catalyst as described in one of claim 1-7, it is characterized in that, in the weight of catalyst for 100%, transition metal is ruthenium, iridium or osmium, transition metal active component presses transition metal weighing scale, the percentage by weight of transition metal active component is 0.1 ~ 10%, further preferably 0.2 ~ 8%, more further preferably 0.3 ~ 3%;
Preferably, described transition metal is the combination of manganese iridium, the mol ratio of described manganese and iridium is 0.01 ~ 0.09, preferably 0.02 ~ 0.04, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 0.1 ~ 10%;
Preferably, described transition metal is the combination of iron ruthenium, the mol ratio of described iron and ruthenium is 0.01 ~ 0.09, preferably 0.02 ~ 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 0.1 ~ 10%;
Preferably, described transition metal is the combination of iron iridium, the mol ratio of described iron and iridium is 0.01 ~ 0.09, preferably 0.02 ~ 0.03, in the weight of catalyst for 100%, transition metal active component presses transition metal weighing scale, and the percentage by weight of transition metal active component is 0.1 ~ 10%;
Preferably, so adjuvant component is the combination of oxide in alkali metal or alkaline-earth metal or any one or at least two kinds in hydroxide, in the weight of catalyst for 100%, the percentage by weight of adjuvant component is 0.1 ~ 40%, further preferably 0.5 ~ 20%, more further preferably 2 ~ 10%.
9. a purposes for the catalyst as described in one of claim 1-8, is characterized in that, described catalyst is used for room temperature purifying formaldehyde.
10. purposes as claimed in claim 9, it is characterized in that, method catalyst being used for room temperature purifying formaldehyde comprises the steps:
First catalytic purification formaldehyde module is prepared by shaping for fine catalyst, then assembling forms catalytic purification formaldehyde assembly, then put it in air purifier or other air cleaning units, under the perturbation action of air, the dusty gas containing formaldehyde is passed through said apparatus, and and catalytic purification component touch, thus the purification of formaldehyde under realizing room temperature.
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| CN108126727A (en) * | 2017-12-19 | 2018-06-08 | 广东省石油与精细化工研究院 | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application |
| CN108187688A (en) * | 2018-01-25 | 2018-06-22 | 北京科技大学 | It is a kind of can be at room temperature by the preparation method of the catalyst of formaldehyde complete catalysts oxidation |
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| CN113797926A (en) * | 2021-10-22 | 2021-12-17 | 中国科学院城市环境研究所 | Formaldehyde catalytic oxidation catalyst and preparation method and application thereof |
| CN113797926B (en) * | 2021-10-22 | 2024-02-02 | 中国科学院城市环境研究所 | Formaldehyde catalytic oxidation catalyst and preparation method and application thereof |
| CN114392736A (en) * | 2022-02-17 | 2022-04-26 | 苏州道一至诚纳米材料技术有限公司 | Catalytic membrane for purifying formaldehyde at normal temperature and preparation method and application thereof |
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| CN115709094A (en) * | 2022-11-14 | 2023-02-24 | 化学与精细化工广东省实验室 | Non-noble metal catalyst for formaldehyde purification and preparation method thereof |
| CN115851024A (en) * | 2022-12-16 | 2023-03-28 | 海啊科技股份有限公司 | Antibacterial and aldehyde-removing spray for automobile foot pads |
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