CN101279238A - Purificant for adsorbing formaldehyde and method of preparing the same - Google Patents
Purificant for adsorbing formaldehyde and method of preparing the same Download PDFInfo
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- CN101279238A CN101279238A CNA2008100276209A CN200810027620A CN101279238A CN 101279238 A CN101279238 A CN 101279238A CN A2008100276209 A CNA2008100276209 A CN A2008100276209A CN 200810027620 A CN200810027620 A CN 200810027620A CN 101279238 A CN101279238 A CN 101279238A
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Abstract
The invention discloses a formaldehyde purificatory absorbent and a preparation method thereof. The main adsorption active component of the formaldehyde adsorption purificant is an aluminum bronze multiple oxide provided with aluminate bronze crystal phase. As a further improvement of the invention, the adsorption active component of the formaldehyde adsorption purificant also comprises a tantalum that is a mixture of one or more of manganese, cobalt, zinc, nickel and iron. The method of the invention adopts the aluminum bronze multiple oxide provided with aluminate bronze crystal phase as the active component of the formaldehyde adsorption purificant; the oxide is of developed pore structure, large specific surface, good thermal stability and is more suitable for the formaldehyde adsorption than alumina as a absorbent owing to the pore structure, thus having better adsorptive performance to the micromolecule of formaldehyde, while the copper atom in the oxide has strong electron adsorption ability and can be combined with the carbonyl group of formaldehyde, thus further improving the adsorption effect to formaldehyde.
Description
Technical field
The present invention relates to a kind of absorption purifier, relate in particular to a kind of purificant for adsorbing formaldehyde, the invention still further relates to the preparation method of this purificant for adsorbing formaldehyde.
Background technology
In recent years, a large amount of artificial harmful chemical gas of making and discharging surrounding air that people are depended on for existence is subjected to severe contamination.In the indoor environment of relative closures such as human settlements building and manned vehicle, owing to a large amount of uses of construction material, finishing material, furniture adhesive and household electrical appliances, office equipment etc., air pollution is particularly serious.According to statistics, the room air chemical contamination is generally tens times of outdoor pollution, in particular cases can reach hundreds of times, can there be 300 kinds more than by detected harmful volatile organic matter, wherein nearly kind more than 20 has strong carcinogenic mutagenesis, it is reported that China is annual because the death toll that room air pollution causes is ten thousand people surplus in the of ten.Wherein the uncomfortable phenomenon of human body that causes of pollutants such as case such as the blood disease that causes with benzo pollutants, leukaemia, pregnant woman's miscarriage, ewborn infant deformity and formaldehyde more sees.As seen indoor air is polluted and has been jeopardized human health, and wherein the uncomfortable phenomenon of human body that causes with pollutants such as formaldehyde is widely known by the people.Investigation shows that the time average that people are in indoor environments such as room, office, vehicle every day is 21.5 hours, near 90% of whole life times.Therefore, the purification techniques of poisonous and harmful substance in the research department improves IAQ, has become one of important topic in the current domestic and international development in science and technology.
At present, Cleaning Technology of Indoor Air mainly contains technology such as ozone treatment, photocatalytic degradation, anion processing and adsorption and purification technology.Wherein, photocatalytic degradation needs enough strong ultraviolet light, and catalytic efficiency is low, is not enough to play desirable catharsis; Ozone technology causes certain injury to people's cognition, should not use in the place that the people arranged; Anion technology can only the local optimum room air, and is limited to the clean-up effect of whole room air.The application experience of developed country such as America and Europe decades shows that adsorption and purification technology is a most important effective method in the room air adsorption and purification technology.
The adsorption and purification technology of room air utilizes active carbon as adsorbent mostly, its internal void structure prosperity, big, the high adsorption capacity of specific area.But active carbon is a kind of non-polar adsorbent, the ability of its absorption apolar substance is stronger, adsorption capacity to polar substances is very little, therefore its absorption only is a kind of physical absorption, though therefore its can absorbing formaldehyde, a large amount of different pollutants of type such as benzene,toluene,xylene, ammonia, carbon monoxide, sulfur dioxide, benzo Bi, but effect is not remarkable, therefore can't make room air reach the purification requirement.Especially little molecule such as formaldehyde and material with acidic nature, the adsorption effect of active carbon is very limited.Therefore, need the cleanser that the higher solution indoor formaldehyde of a kind of efficient of exploitation pollutes badly.
Summary of the invention
The object of the present invention is to provide that a kind of adsorbance is big, the purificant for adsorbing formaldehyde of good stability.
Another object of the present invention provides the preparation method of the simple purificant for adsorbing formaldehyde of a kind of technology.
The invention provides a kind of purificant for adsorbing formaldehyde, it is characterized in that: the main adsorption activity component of described purificant for adsorbing formaldehyde is the copper aluminium composite oxide with cupric aluminate crystalline phase.Cupric aluminate has better adsorption cleaning performance than simple cupric oxide or aluminium oxide, because cupric aluminate had both kept the flourishing pore structure of aluminum oxide, and simultaneously the ability of copper atom with stronger attract electrons provides new adsorption potential for absorbing formaldehyde.
The copper in the copper aluminium composite oxide of the present invention and the mol ratio of aluminium are 1: 100～10: 1, the mol ratio of copper and aluminium is controlled in this scope, make this copper aluminium composite oxide can form stable cupric aluminate crystalline phase like this, if both mol ratio of copper and aluminium then forms CuO and Al respectively greater than aforementioned proportion
2O
3Crystalline phase, the content of corresponding cupric aluminate seldom decrease for the absorption property of formaldehyde.
The present invention can be further improved, and promptly adds other metallic elements in the adsorption activity component of purificant for adsorbing formaldehyde, described other metallic elements be manganese, cobalt, zinc, nickel and iron in one or more mixture.The molar content of described other metallic elements is 10～40% of an absorption purifier gross mass.In absorption purifier, these metallic elements exist with the form of metal oxide, acid oxide or basic oxide, can play the activated adoption position that increases in the metal oxide, and then strengthen its adsorption cleaning effect for formaldehyde.
The present invention also provides a kind of preparation method of purificant for adsorbing formaldehyde, and it may further comprise the steps:
(1) gets mantoquita in proportion and aluminium salt is water-soluble, and add thermal agitation in 25～60 ℃ water-bath and fully dissolve, make the mixed solution of mantoquita and aluminium salt;
(2) get the inorganic base stirring and dissolving in addition in water, make inorganic alkali solution;
(3) mixed solution of above-mentioned mantoquita and aluminium salt and inorganic alkali solution are carried out under constantly stirring and flow the co-precipitation titration, obtain suspension after titration is finished, proceed abundant stirring; Then with suspension ageing 2～4 hours under 25～60 ℃ of conditions;
(4) suspension filtered after filter residue spends deionised water, is dried under 100～140 ℃ of conditions of temperature earlier, 300～1200 ℃ of roastings 5～15 hours, obtains purificant for adsorbing formaldehyde again.
In the technique scheme, in the step (1) except that getting mantoquita and aluminium salt, also can increase other metallic element salt, wherein said other metallic elements be manganese, cobalt, zinc, nickel and iron in one or more mixture, the molar content of described other metallic elements is the 10-40% of absorption purifier gross mass.
Inorganic base described in the step (2) is one or more the mixture in hydroxide, carbonate, subcarbonate and the ammoniacal liquor.Wherein inorganic base can be selected one or more the mixture in NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, potash, sodium acid carbonate, saleratus, sodium acid carbonate and the ammoniacal liquor for use.
When carrying out and flow the co-precipitation titration, should control flow velocity and guarantee that the titration simultaneously of two solution finishes, and after titration finishes, proceeds sufficient stirring in the step (3).
Compared with prior art, advantage of the present invention is:
(1) the present invention adopts and has the adsorbent activity composition of the copper aluminium composite oxide of cupric aluminate crystalline phase as formaldehyde, the pore structure of this oxide is very flourishing, big and the Heat stability is good of specific area, and pore structure is more suitable than aluminium oxide with respect to formaldehyde absorption, thereby the micromolecular absorption property of PARA FORMALDEHYDE PRILLS(91,95) is good, and the copper atom with strong electron-withdrawing power in the oxide can combine with the carbonyl of formaldehyde, thereby further improves the adsorption effect of PARA FORMALDEHYDE PRILLS(91,95).
(2) absorption purifier of the present invention adopts and the preparation of stream coprecipitation, to splash into the concentration of formation simultaneously close for metal salt solution and inorganic alkali solution during operation, both react the environment that generates precipitation and are tending towards neutral, make the reaction of slaine and aqueous slkali form the predecessor of composite oxides such as oxide such as hydroxide, carbonate, bicarbonate, subcarbonate, hydroxide hydrate earlier, thereby obtain sedimentation effect preferably, the metal combination stability and the crystalline phase stability of the absorption purifier for preparing are higher, adsorption effect is more stable, the product quality height.
(3) step (4) among the preparation method of the present invention is the process of metal oxide crystalline phase formation, and washing process separates slaine or the inorganic base that is mingled with in the precipitation mixture, avoids forming in the last heat treatment process impurity phase.
The specific embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is set forth, and protection scope of the present invention is not only to be confined to following examples.The those of ordinary skill of described technical field all can be realized purpose of the present invention according to content disclosed by the invention.
Embodiment 1
Prepare purificant for adsorbing formaldehyde by following step:
(1) takes by weighing 37.5g aluminum nitrate and 19.9g Schweinfurt green, add 200ml water and carry out stirring and dissolving, obtain the mixed solution of aluminum nitrate and Schweinfurt green in 30 ℃ water-bath heating;
(2) take by weighing 20g NaOH, add 100ml water and dissolve, obtain sodium hydroxide solution;
(3) mixed solution and the sodium hydroxide solution with aluminum nitrate, Schweinfurt green places dropping funel respectively, placement one has the beaker of 100mL water below the dropping funel, paddle is placed in the beaker, open agitator, carry out under constantly stirring and flow the co-precipitation titration, the control flow velocity guarantees that the while titration of two solution finishes, after titration finishes, proceed sufficient stirring, and room temperature ageing 4 hours;
(4) suspension is carried out suction filtration, filter residue spends deionised water twice, places 100 ℃ baking oven to carry out drying then, again dried powder is put into Muffle furnace, roasting is 10 hours under 500 ℃ of conditions of temperature, obtains the purificant for adsorbing formaldehyde sample, is labeled as A.
Get 8g purificant for adsorbing formaldehyde A and place 800 liters of glass capsulation cabins, measure 1ml formaldehyde with pipette and join in the glass capsulation cabin, with the hatchcover sealing, carried out the analysis of concentration of formaldehyde every one hour then.The analysis of concentration of formaldehyde adopts Interscan 4160 type formaldehyde analyzers to carry out, and adopts AAS to demarcate, and the adsorption cleaning of formaldehyde the results are shown in table 1.
Embodiment 2
Prepare purificant for adsorbing formaldehyde by following step:
(1) takes by weighing 23.5g aluminum nitrate and 19.9g Schweinfurt green, add 200ml water and carry out stirring and dissolving, obtain the mixed solution of aluminum nitrate and Schweinfurt green in 35 ℃ water-bath heating;
(2) take by weighing 32.01g sodium carbonate, add 100ml water and dissolve, obtain sodium carbonate liquor;
(3) slaine mixed solution and sodium carbonate liquor are placed dropping funel respectively, placement one has the beaker of 100mL water below the dropping funel, paddle is placed in the beaker, open agitator, carry out under constantly stirring and flow the co-precipitation titration, the control flow velocity guarantees that the while titration of two solution finishes, after titration finishes, proceed sufficient stirring, and ageing 4 hours under 20 ℃ of temperature;
(4) suspension is carried out suction filtration, filter residue spends deionised water twice, places 120 ℃ baking oven to carry out drying then, again dried powder is put into Muffle furnace, roasting is 10 hours under 300 ℃ of conditions of temperature, obtains the purificant for adsorbing formaldehyde sample, is labeled as B.
Carry out the absorption purifying effect test of formaldehyde by the method among the embodiment 1, the results are shown in table 1.
Embodiment 3
Prepare purificant for adsorbing formaldehyde by following step:
(1) takes by weighing 37.5g aluminum nitrate and 9.9g Schweinfurt green, add 200ml water and carry out stirring and dissolving, obtain the mixed solution of aluminum nitrate and Schweinfurt green in 30 ℃ water-bath heating;
(2) take by weighing 16g NaOH, add 100ml water and dissolve, obtain sodium hydroxide solution;
(3) slaine mixed solution and sodium hydroxide solution are placed dropping funel respectively, placement one has the beaker of 100mL water below the dropping funel, paddle is placed in the beaker, open agitator, carry out under constantly stirring and flow the co-precipitation titration, the control flow velocity guarantees that the while titration of two solution finishes, after titration finishes, proceed sufficient stirring, and ageing 4 hours under 40 ℃ of temperature;
(4) suspension is carried out suction filtration, filter residue spends deionised water twice, places 120 ℃ baking oven to carry out drying then, again dried powder is put into Muffle furnace, roasting is 10 hours under 800 ℃ of conditions of temperature, obtains the purificant for adsorbing formaldehyde sample, is labeled as C.
Carry out the absorption purifying effect test of formaldehyde by the method among the embodiment 1, the results are shown in table 1.
Embodiment 4
Prepare purificant for adsorbing formaldehyde by following step:
(1) take by weighing 3.75g aluminum nitrate, 1.99g copper sulphate and 0.20g manganese acetate, 0.20g nickel acetate respectively, the 0.20g cobalt acetate dissolves jointly, adds 200ml water and carries out stirring and dissolving in 40 ℃ water-bath heating, obtains the mixed solution of aluminum nitrate and Schweinfurt green;
(2) take by weighing 10.5g sodium carbonate, add 100ml water and dissolve, obtain sodium carbonate liquor;
(3) slaine mixed solution and sodium carbonate liquor are placed dropping funel respectively, placement one has the beaker of 100mL water below the dropping funel, paddle is placed in the beaker, open agitator, carry out under constantly stirring and flow the co-precipitation titration, the control flow velocity guarantees that the while titration of two solution finishes, after titration finishes, proceed sufficient stirring, and room temperature ageing 2 hours;
(4) suspension is carried out suction filtration, filter residue spends deionised water twice, places 120 ℃ baking oven to carry out drying then, again dried powder is put into Muffle furnace, roasting is 10 hours under 1200 ℃ of conditions of temperature, obtains the purificant for adsorbing formaldehyde sample, is labeled as D.
Carry out the absorption purifying effect test of formaldehyde by the method among the embodiment 1, the results are shown in table 1.
Embodiment 5
Prepare purificant for adsorbing formaldehyde by following step:
(1) takes by weighing 3.75g aluminum nitrate, 1.99g copper sulphate, 0.20g manganese sulfate respectively and dissolve jointly, add 200ml water and carry out stirring and dissolving, obtain the mixed solution of aluminum nitrate and Schweinfurt green in 30 ℃ water-bath heating;
(2) take by weighing 10.25g sodium carbonate, add 100ml water and dissolve, obtain sodium carbonate liquor;
(3) slaine mixed solution and sodium carbonate liquor are placed dropping funel respectively, placement one has the beaker of 100mL water below the dropping funel, paddle is placed in the beaker, open agitator, carry out under constantly stirring and flow the co-precipitation titration, the control flow velocity guarantees that the while titration of two solution finishes, after titration finishes, proceed sufficient stirring, and room temperature ageing 3 hours;
(4) suspension is carried out suction filtration, filter residue spends deionised water twice, places 140 ℃ baking oven to carry out drying then, again dried powder is put into Muffle furnace, roasting is 10 hours under 900 ℃ of conditions of temperature, obtains the purificant for adsorbing formaldehyde sample, is labeled as E.
Carry out the absorption purifying effect test of formaldehyde by the method among the embodiment 1, the results are shown in table 1.
Table 1
| Adsorbent | Initial concentration of formaldehyde (mg/m3) | 1h concentration (mg/m3) | 3h concentration (mg/m3) | 8h concentration (mg/m3) | 24h concentration (mg/m3) |
| A | 1.52 | 0.80 | 0.22 | 0.09 | 0.06 |
| B | 1.88 | 0.62 | 0.36 | 0.11 | 0.07 |
| C | 1.96 | 0.92 | 0.24 | 0.09 | 0.09 |
| D | 1.46 | 1.03 | 0.61 | 0.46 | 0.14 |
| E | 2.20 | 1.64 | 1.20 | 0.44 | 0.11 |
| Active carbon | 1.68 | 1.32 | 1.30 | 1.33 | 1.35 |
Table 1 as can be seen, the adsorption effect of purificant for adsorbing formaldehyde PARA FORMALDEHYDE PRILLS(91,95) provided by the invention all is better than the adsorption effect of active carbon.
Claims (10)
1, a kind of purificant for adsorbing formaldehyde is characterized in that: the main adsorption activity component of described purificant for adsorbing formaldehyde is the copper aluminium composite oxide with cupric aluminate crystalline phase.
2, purificant for adsorbing formaldehyde according to claim 1 is characterized in that: the copper in the described copper aluminium composite oxide and the mol ratio of aluminium are 1: 100～10: 1.
3, purificant for adsorbing formaldehyde according to claim 1 and 2 is characterized in that: the adsorption activity component of described purificant for adsorbing formaldehyde also includes other metallic elements.
4, purificant for adsorbing formaldehyde according to claim 3 is characterized in that: described other metallic elements be manganese, cobalt, zinc, nickel and iron in one or more mixture.
5, purificant for adsorbing formaldehyde according to claim 4 is characterized in that: the molar content of described other metallic elements is 10～40% of an absorption purifier gross mass.
6, the preparation method of a kind of claim 1 or 2 described purificant for adsorbing formaldehyde, it may further comprise the steps:
(1) gets mantoquita in proportion and aluminium salt is water-soluble, and add thermal agitation in 25～60 ℃ water-bath and fully dissolve, make the mixed solution of mantoquita and aluminium salt;
(2) get the inorganic base stirring and dissolving in addition in water, make inorganic alkali solution;
(3) mixed solution of above-mentioned mantoquita and aluminium salt and inorganic alkali solution are carried out under constantly stirring and flow the co-precipitation titration, obtain suspension after titration is finished, proceed abundant stirring; Then with suspension ageing 2～4 hours under 25～60 ℃ of conditions;
(4) suspension filtered after filter residue spends deionised water, is dried under 100～140 ℃ of conditions of temperature earlier, 300～1200 ℃ of roastings 5～15 hours, obtains purificant for adsorbing formaldehyde again.
7, the preparation method of purificant for adsorbing formaldehyde according to claim 6 is characterized in that: except that getting mantoquita and aluminium salt, also got other metallic element salt in the step (1); The molar content of described other metallic elements is the 10-40% of absorption purifier gross mass.
8, the preparation method of purificant for adsorbing formaldehyde according to claim 7 is characterized in that: described other metallic elements be manganese, cobalt, zinc, nickel and iron in one or more mixture.
9, the preparation method of purificant for adsorbing formaldehyde according to claim 6 is characterized in that: the inorganic base described in the step (2) is one or more the mixture in hydroxide, carbonate, subcarbonate and the ammoniacal liquor.
10, the preparation method of purificant for adsorbing formaldehyde according to claim 6 is characterized in that: when carrying out and flow the co-precipitation titration, should control flow velocity and guarantee that the titration simultaneously of two solution finishes, and after titration finishes, proceeds sufficient stirring in the step (3).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103599793A (en) * | 2013-11-28 | 2014-02-26 | 天津市环境保护科学研究院 | Supported copper-manganese composite oxide catalyst capable of removing formaldehyde at room temperature and preparation method |
| CN104607154A (en) * | 2015-01-06 | 2015-05-13 | 福建省林业科学研究院 | Method for preparing adsorbent by modifying tea by-product with hansenula microbes |
| CN104857840A (en) * | 2014-02-26 | 2015-08-26 | 绿普达(北京)科技有限公司 | Novel purifying material for removing indoor formaldehyde and common peculiar smell and preparation method therefor |
| CN104888694A (en) * | 2015-05-28 | 2015-09-09 | 同济大学 | Adsorbing material for efficiently adsorbing indoor formaldehyde and methylbenzene gases |
| CN106139895A (en) * | 2016-08-15 | 2016-11-23 | 季红军 | A kind of preparation method removing formaldehyde composite |
| CN107298581A (en) * | 2017-06-02 | 2017-10-27 | 浙江大学 | The preparation method of cupric aluminate spinelle porous blocks |
| CN113398752A (en) * | 2021-06-22 | 2021-09-17 | 深圳特沃德环保科技有限公司 | Air purification material with formaldehyde removal effect and preparation method thereof |
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2008
- 2008-04-23 CN CNA2008100276209A patent/CN101279238A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599793A (en) * | 2013-11-28 | 2014-02-26 | 天津市环境保护科学研究院 | Supported copper-manganese composite oxide catalyst capable of removing formaldehyde at room temperature and preparation method |
| CN104857840A (en) * | 2014-02-26 | 2015-08-26 | 绿普达(北京)科技有限公司 | Novel purifying material for removing indoor formaldehyde and common peculiar smell and preparation method therefor |
| CN104857840B (en) * | 2014-02-26 | 2017-09-01 | 绿普达(北京)科技有限公司 | A kind of scavenging material for removing indoor formaldehyde and common peculiar smell and preparation method thereof |
| CN104607154A (en) * | 2015-01-06 | 2015-05-13 | 福建省林业科学研究院 | Method for preparing adsorbent by modifying tea by-product with hansenula microbes |
| CN104607154B (en) * | 2015-01-06 | 2017-04-26 | 福建省林业科学研究院 | Method for preparing adsorbent by modifying tea by-product with hansenula microbes |
| CN104888694A (en) * | 2015-05-28 | 2015-09-09 | 同济大学 | Adsorbing material for efficiently adsorbing indoor formaldehyde and methylbenzene gases |
| CN106139895A (en) * | 2016-08-15 | 2016-11-23 | 季红军 | A kind of preparation method removing formaldehyde composite |
| CN106139895B (en) * | 2016-08-15 | 2018-09-04 | 广州洁宜日化用品有限公司 | A kind of preparation method for removing formaldehyde composite material |
| CN107298581A (en) * | 2017-06-02 | 2017-10-27 | 浙江大学 | The preparation method of cupric aluminate spinelle porous blocks |
| CN107298581B (en) * | 2017-06-02 | 2020-10-30 | 浙江大学 | Method for preparing porous block of copper aluminate spinel |
| CN113398752A (en) * | 2021-06-22 | 2021-09-17 | 深圳特沃德环保科技有限公司 | Air purification material with formaldehyde removal effect and preparation method thereof |
| CN113398752B (en) * | 2021-06-22 | 2022-01-11 | 深圳特沃德环保科技有限公司 | Air purification material with formaldehyde removal effect and preparation method thereof |
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