CN109225140A - A kind of modification is except formaldehyde zeolite and preparation method thereof - Google Patents
A kind of modification is except formaldehyde zeolite and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/20707—Titanium
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Abstract
The present invention provides a kind of modifications to remove formaldehyde zeolite, is fixed with TiO in zeolite2And MnO2, zeolite surface is modified with hydrophobic group.Additionally provide this preparation method except formaldehyde zeolite simultaneously, step includes: (1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows: TiO2For 0.01%-10%, MnO2For 0.01-10%, ammonium hydroxide 0.1-10%, ethyl alcohol 25-60%；(2) the hydrophobic organosilicon alkanes material of ethyl orthosilicate sum is added in the solution that step (1) obtains, it is dry after mixing；(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: powder 0.1-10%, NaAlO after dry2It is dried after stirring for 0.1-10%, NaOH 0.1-10%.The modification that the present invention obtains except formaldehyde zeolite be utilized simultaneously titanium dioxide with its activity height, thermal stability is good, formaldehyde can be catalytically decomposed as CO at room temperature for cheap, harmless and manganese dioxide2And H2The characteristics of O, can efficiently remove formaldehyde.
Description
Technical field
The present invention relates to formaldehyde absorbing catalysis technical fields, and in particular to a kind of modification removes formaldehyde zeolite and its preparation side
Method.
Background technique
Formaldehyde is a kind of carcinogen, is hidden in human lives, such as plate, cabinet, emulsion paint, adhesive etc..
Except there are mainly two types of methods at present for formaldehyde: physisorphtion and catalytic decomposition.Physisorphtion mainly uses
Various porous medias pass through the method that suction-operated removes indoor formaldehyde.Adsorbent generally has following characteristics: large specific surface area,
For porous structure；There is stronger adsorption capacity to adsorbate；It is not chemically reacted with medium；It is easily manufactured, regenerating easily etc..
Common adsorbent has silica gel, aluminium oxide, magnesia, calcium carbonate, active carbon, zeolite molecular sieve, diatomite etc..But merely
Some inevitable disadvantages of physical absorption, low efficiency, stability are poor, be easy to fall off, by temperature and concentration of formaldehyde influenced compared with
Greatly.People are often to be modified to porous media solving these problems at present, to strengthen their absorption effect
Fruit.
Catalytic decomposition formaldehyde is another effective means for removing formaldehyde, common such as photocatalyst.Photocatalyst is a kind of in light
Under irradiation, itself does not change, and can but promote the substance of chemical reaction, and photocatalyst is converted using luminous energy existing for nature
The oxygen of surrounding and hydrone is set to be excited into great oxidizing force to generate catalytic action as energy needed for chemical reaction
Free anion.All pairs of human bodies of almost separable solution and the harmful organic substance of environment and part inorganic substances, can not only use
The law of nature accelerates reaction, and the wasting of resources and additional pollution will not be caused to be formed.In numerous photochemical catalysts, Ti02
The advantages that activity is high, thermal stability is good, cheap, harmless with it is known as being optimal environmental improvement photocatalysis
Agent.
Have currently on the market and catalyst is used in combination with adsorbent material, but there is problems in that (1) adsorbent material is negative
Carried catalyst, adsorbent material can quickly absorb moisture in wet air, and causing catalyst to be covered with water causes catalyst living
Property decline or failure；(2) catalyst is largely photocatalyst, such as Ti02, but photocatalyst needs to absorb ultraviolet photoactivation and urges
Change performance, so needing the irradiation of ultraviolet light in routine use, this point limits material and applies in practice.
So formaldehyde can efficiently be removed and can effectively overcome the material of disadvantages mentioned above by being badly in need of one kind.
Summary of the invention
Technical problem to be solved of the invention is that modified formaldehyde zeolite can efficiently be removed by providing one kind, and provides
The preparation method of this modified zeolite.
The present invention solves above-mentioned technical problem using following technical scheme:
A kind of modification removes formaldehyde zeolite, is fixed with TiO in the zeolite2And MnO2, the zeolite surface is modified with hydrophobic
Group.
Further, the hydrophobic group is alkyl chain.
This modification removes the preparation method of formaldehyde zeolite, mainly includes the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and be stirred, make the mass concentration of its each substance such as
Under: TiO2For 0.01%-10%, MnO2For 0.01-10%, ammonium hydroxide 0.1-10%, ethyl alcohol 25-60%；
(2) the hydrophobic organosilicon alkanes material of ethyl orthosilicate sum is added in the solution that step (1) obtains, control is just
The mass concentration of silester is 0.1-10%, and the mass concentration of hydrophobic organosilicon alkanes material is 0.05-5%, after mixing
It is dry；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 0.1-10%, NaAlO2It is dried after stirring for 0.1-10%, NaOH 0.1-10%.
Further, the temperature being stirred in the step (1) is room temperature, and the time being stirred is 0.5-2h.
Further, organosilicon alkanes material includes trimethyl silane, tetramethylsilane, benzyl three in the step (2)
Methyl-monosilane, (methoxy) trimethyl silane, (trifluoromethyl) trimethyl silane, phenylene-ethynylene trimethyl silane, 3-
Aminopropyl trimethoxylsilane, triethylsilane, tetraethyl silane, methyl triethylsilane, dimethyl ethyl silane, dimethyl
Phenethyl silane, ethyl dimethylchlorosilane, dichloromethyl (2- phenethyl) silane, two (1- Methylethyl)-silane, (N, N-
Dimethylamino) triethylsilane, one or more of phenylethyltrichlorosilane and dimethyl diethylsilane.
Further, the mode/means mixed in the step (2) are that 5-20h is stirred at room temperature.
Further, drying mode/means in the step (2) are as follows: 1-8h is first dried in a vacuum, then in 90-110
Dry 2-10h in the environment of DEG C.
Further, whipping temp is room temperature, mixing time 4-24h in the step (3).
Further, the mode/means dried in the step (3) are as follows: turn the gel obtained after stirring in step (3)
Teflon on piece is moved on to, first in 90-110 DEG C of drying 22-26h；Then it is rinsed with a large amount of water, in the environment of 90-110 DEG C
Dry 10-14h.
The present invention has the advantages that
The present invention provides what a kind of catalyst was used in combination with adsorbent material to remove formaldehyde materials, by the inside of zeolite
Titanium dioxide and manganese dioxide is added, and is modified with hydrophobic grouping in zeolite surface, while titanium dioxide is utilized with its activity
Height, thermal stability are good, formaldehyde can be catalytically decomposed as CO at room temperature for cheap, harmless and manganese dioxide2With
H2The characteristics of O；In addition, this zeolite can also effectively overcome adsorbent material that can quickly absorb moisture in wet air, lead
Catalyst is caused to be covered with water the disadvantages of leading to catalyst activity reduction or failure.
Specific embodiment
The present invention will be further described With reference to embodiment, following embodiment be intended to illustrate invention without
It is limitation of the invention further.
Raw material of the present invention can synthesize commercially or according to the prior art.
A kind of modification of the invention removes formaldehyde zeolite, is fixed with TiO in the zeolite2And MnO2, the zeolite surface modification
There is hydrophobic group.
Embodiment 1
A kind of modification removes the preparation method of formaldehyde zeolite, comprising the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows:
TiO2For 0.01%, MnO2It is 0.01%, ammonium hydroxide 0.1%, ethyl alcohol 30% stirs 0.5h at room temperature；
(2) ethyl orthosilicate and trimethyl silane are added in the solution that step (1) obtains, controls the matter of ethyl orthosilicate
Measuring concentration is 0.1%, and the concentration of trimethyl silane is 0.05%, continues that 5h is stirred at room temperature；1h is first dried in a vacuum, removes water
And ethyl alcohol obtains powder then in 90 DEG C of dry 2h；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 0.1%, NaAlO2For 0.1%, NaOH 0.1%, 4h is stirred at room temperature, the gel obtained after stirring is shifted
To Teflon on piece, first in 90 DEG C of drying 22h；Then it is rinsed with a large amount of water, is had in 90 DEG C of drying 10h to get to load
TiO2And MnO2Zeolite, while zeolite surface has hydrophobic grouping modification.
Embodiment 2:
A kind of modification removes the preparation method of formaldehyde zeolite, comprising the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows:
TiO2For 0.2%, MnO2It is 0.2%, ammonium hydroxide 0.8%, ethyl alcohol 42% stirs 0.5h at room temperature；
(2) ethyl orthosilicate and dimethyl diethoxysilane are added in the solution that step (1) obtains, controls positive silicic acid
The mass concentration of ethyl ester is 2%, and the mass concentration of dimethyl diethoxysilane is 0.2%, continues that 8h is stirred at room temperature；First true
The dry 4h of sky, removes water and ethyl alcohol then in 100 DEG C of dry 8h and obtains powder；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 1.6%, NaAlO2For 1%, NaOH 1.5%, 12h is stirred at room temperature, the gel obtained after stirring is shifted
To Teflon on piece, dried for 24 hours at 100 DEG C first；Then it is rinsed with a large amount of water, is had in 100 DEG C of drying 12h to get to load
TiO2And MnO2Zeolite, while zeolite surface has hydrophobic grouping modification.
Embodiment 3:
A kind of modification removes the preparation method of formaldehyde zeolite, comprising the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows:
TiO2For 1%, MnO2It is 0.5%, ammonium hydroxide 4%, ethyl alcohol 50% stirs 2h at room temperature；
(2) ethyl orthosilicate and trimethyl silane are added in the solution that step (1) obtains, controls the matter of ethyl orthosilicate
Measuring concentration is 3%, and the concentration of trimethyl silane is 1.5%, continues that 12h is stirred at room temperature；First in vacuum drying 6h, water and second are removed
Alcohol obtains powder then in 100 DEG C of dry 8h；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 1.3%, NaAlO2For 0.6%, NaOH 1%, 12h is stirred at room temperature, the gel obtained after stirring is shifted
To Teflon on piece, dried for 24 hours at 100 DEG C first；Then it is rinsed with a large amount of water, is had in 100 DEG C of drying 12h to get to load
TiO2And MnO2Zeolite, while zeolite surface has hydrophobic grouping modification.
Embodiment 4:
A kind of modification removes the preparation method of formaldehyde zeolite, comprising the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows:
TiO2For 2%, MnO2It is 1%, ammonium hydroxide 6%, ethyl alcohol 50% stirs 4h at room temperature；
(2) triethylsilane of ethyl orthosilicate and 1.5% is added in the solution that step (1) obtains, controls positive silicic acid
The mass concentration of ethyl ester is 3%, and the mass concentration of triethylsilane is 1.5%, continues that 12h is stirred at room temperature；First it is being dried in vacuo
6h removes water and ethyl alcohol then in 100 DEG C of dry 10h and obtains powder；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 1.6%, NaAlO2For 0.8%, NaOH 1.3%, 12h is stirred at room temperature, the gel obtained after stirring is turned
Teflon on piece is moved on to, is dried for 24 hours at 100 DEG C first；Then with a large amount of water rinse, 100 DEG C of drying 12h to get to load
There is TiO2And MnO2Zeolite, while zeolite surface has hydrophobic grouping modification.
Embodiment 5:
A kind of modification removes the preparation method of formaldehyde zeolite, comprising the following steps:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and mix, keep the mass concentration of its each substance as follows:
TiO2For 10%, MnO2It is 10%, ammonium hydroxide 10%, ethyl alcohol 60% stirs 2h at room temperature；
(2) ethyl orthosilicate and benzyl trimethyl silane are added in the solution that step (1) obtains, controls ethyl orthosilicate
Mass concentration be 10%, the mass concentration of benzyl trimethyl silane is 5%, continues that 20h is stirred at room temperature；First it is dried in a vacuum
8h removes water and ethyl alcohol then in 110 DEG C of dry 10h and obtains powder；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: is dry
Powder afterwards is 10%, NaAlO2For 10%, NaOH 10%, it is stirred at room temperature for 24 hours, the gel obtained after stirring is transferred to
Teflon on piece, first in 110 DEG C of drying 26h；Then it is rinsed with a large amount of water, is had in 110 DEG C of drying 14h to get to load
TiO2And MnO2Zeolite, while zeolite surface has hydrophobic grouping modification.
Further, the hydrophobic organosilicon alkanes material selected in above-described embodiment is not limited to trimethyl silane, two
Methyldiethoxysilane, triethylsilane and base trimethyl silane；It is also possible to trimethyl silane, tetramethylsilane, benzyl
Trimethyl silane, (methoxy) trimethyl silane, (trifluoromethyl) trimethyl silane, phenylene-ethynylene trimethyl silane,
3- aminopropyl trimethoxylsilane, triethylsilane, tetraethyl silane, methyl triethylsilane, dimethyl ethyl silane, diformazan
Base phenethyl silane, ethyl dimethylchlorosilane, dichloromethyl (2- phenethyl) silane, two (1- Methylethyl)-silane, (N,
N- dimethylamino) triethylsilane, one or more of phenylethyltrichlorosilane and dimethyl diethylsilane.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme；Those skilled in the art should understand that still can modify to the present invention or equivalent replacement；And all are not
It is detached from the technical solution and its improvement of the spirit and scope of the present invention, should all be covered within the scope of the claims of the present invention.
Claims (9)
1. a kind of modification removes formaldehyde zeolite, which is characterized in that be fixed with TiO in the zeolite2And MnO2, the zeolite surface repairs
It is decorated with hydrophobic group.
2. a kind of modification according to claim 1 removes formaldehyde zeolite, which is characterized in that the hydrophobic group is alkyl
Chain.
3. the preparation method that a kind of modification as claimed in claim 1 or 2 removes formaldehyde zeolite, which is characterized in that mainly include with
Lower step:
(1) by TiO2、MnO2, ammonium hydroxide and ethyl alcohol be added in pure water and be stirred, keep the mass concentration of its each substance as follows:
TiO2For 0.01%-10%, MnO2For 0.01-10%, ammonium hydroxide 0.1-10%, ethyl alcohol 25-60%；
(2) the hydrophobic organosilicon alkanes material of ethyl orthosilicate sum is added in the solution that step (1) obtains, controls positive silicic acid
The mass concentration of ethyl ester is 0.1-10%, and the mass concentration of hydrophobic organosilicon alkanes material is 0.05-5%, dry after mixing；
(3) powder, NaAlO after taking drying2It is added to the water with NaOH, keeps the mass concentration of its each substance as follows: the powder after dry
End is 0.1-10%, NaAlO2It is dried after stirring for 0.1-10%, NaOH 0.1-10%.
4. preparation method according to claim 3, which is characterized in that the temperature being stirred in the step (1) is room
Temperature, the time being stirred are 0.5-2h.
5. preparation method according to claim 3, which is characterized in that organosilicon alkanes material includes in the step (2)
Trimethyl silane, tetramethylsilane, benzyl trimethyl silane, (methoxy) trimethyl silane, (trifluoromethyl) trimethyl
Silane, phenylene-ethynylene trimethyl silane, 3- aminopropyl trimethoxylsilane, triethylsilane, tetraethyl silane, three second of methyl
Base silane, dimethyl ethyl silane, dimethylphenethyl silane, ethyl dimethylchlorosilane, dichloromethyl (2- phenethyl) silicon
Alkane, two (1- Methylethyl)-silane, (N, N- dimethylamino) triethylsilane, phenylethyltrichlorosilane and dimethyl diethyl
One or more of base silane.
6. preparation method according to claim 3, which is characterized in that the mode/means mixed in the step (2) be
5-20h is stirred at room temperature.
7. preparation method according to claim 3, which is characterized in that dry mode/means are in the step (2):
1-8h is first dried in a vacuum, then the dry 2-10h under 90-110 DEG C of environment.
8. preparation method according to claim 3, which is characterized in that whipping temp is room temperature, stirring in the step (3)
Time is 4-24h.
9. preparation method according to claim 3, which is characterized in that the mode/means dried in the step (3) are:
The gel obtained after stirring in step (3) is transferred to Teflon on piece, first in 90-110 DEG C of drying 22-26h；Then with big
The water of amount rinses, and dries 10-14h under 90-110 DEG C of environment.
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| CN111974156A (en) * | 2019-05-24 | 2020-11-24 | 宁夏大学 | Preparation method of scavenger for efficiently degrading gaseous pollutants |
| CN112121765A (en) * | 2020-09-24 | 2020-12-25 | 张艺峰 | Environment-friendly formaldehyde-removing activated carbon and preparation method thereof |
| CN113181895A (en) * | 2021-04-29 | 2021-07-30 | 陕西科技大学 | Silicon-based composite material with photocatalysis aldehyde removal function and preparation method thereof |
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| CN113181895A (en) * | 2021-04-29 | 2021-07-30 | 陕西科技大学 | Silicon-based composite material with photocatalysis aldehyde removal function and preparation method thereof |
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Inventor after: Liu Hui Inventor before: Hu Xiao Inventor before: Liu Hui |
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Application publication date: 20190118 |