CN1631514A - Metal supporting carbon absorbent for removing aldehyde and its preparing process - Google Patents
Metal supporting carbon absorbent for removing aldehyde and its preparing process Download PDFInfo
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- CN1631514A CN1631514A CN 200410068068 CN200410068068A CN1631514A CN 1631514 A CN1631514 A CN 1631514A CN 200410068068 CN200410068068 CN 200410068068 CN 200410068068 A CN200410068068 A CN 200410068068A CN 1631514 A CN1631514 A CN 1631514A
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- transition metal
- metal salt
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- formaldehyde
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Abstract
The invention unfurls a kind of attaching dose and its producing way. The invention adds the excessive metal salt in the mixing solution, mix them, then spin silk, prepare to oxidize, carbonize and activate; or add the excessive metal salt in the unit solution, then mix, spin silk, prepare to oxidize, carbonize and activate, get the carbon attaching dose. The invention is applied in taking off aldehyde, it has catalyzing feature, so the efficiency is increased largely. The way has no pollution in taking off aldehyde, high efficiency, large capacity; the result is better than normal attaching dose of holes.
Description
Technical field
The present invention relates to a kind of adsorbent, particularly a kind of carrying transition metal salt, be used to carbon absorbent that removes aldehyde-containing gas and preparation method thereof.
Background technology
In recent years, formaldehyde pollutes a key factor that becomes indoor pollution.Formaldehyde is a kind of VOC (VOC-Volatile Organic Compounds), and administering formaldehyde pollution becomes a major part of administering indoor VOC pollution.In order fundamentally to solve the pollution that VOC caused such as formaldehyde, the method for absorption commonly used.
Carbon absorbent is the adsorbent of using always.The adsorption capacity of carbon absorbent is subjected to the influence of its pore structure and surface chemistry environment.Traditional carbon absorbent is normally formed by low-temperature carbonization, high-temperature activation when water vapour or carbon dioxide or their mist are activator by organic fiber, is a kind of non-polar adsorbent.Numerous carbon absorbents makes it be suitable for the absorption to low polar molecule such as hydrocarbon because its nonpolar surface, but for polar molecule, just seems not too suitable as the absorption of gaseous aldehyde, and removal efficiency is low, and adsorption capacity is little.
The technical issues that need to address of the present invention are carbon absorbent for removing aldehyde that disclose a kind of carried metal and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The carbon absorbent for removing aldehyde of carried metal of the present invention is a kind of fibrous carbonaceous adsorbent, and its component and weight percent content are:
Polymer 95～99.9999%
Transition metal 0.0001～5%
Said polymer is selected from cellulose, polyacrylonitrile, pitch or phenolic resins;
Preferred transition metal is selected from copper, iron, cobalt, nickel or manganese.
One of preparation method of the carbon absorbent for removing aldehyde of carried metal of the present invention comprises the steps:
Transition metal salt solution is mixed with polymer solution, adopt the dustless spinning of method well known in the art, pre-oxidation, charing, activation then, make the carbon absorbent of carried metal;
Said method well known in the art all has description on general textbook and relevant technical manual, the present invention repeats no more.
Said transition metal salt is selected from sulfate, nitrate, acetate or the halide of transition metal;
Preferably cross slaine and be selected from copper, iron, cobalt, nickel or manganese;
The weight concentration of transition metal salt solution is 0.001%-10%;
In the gross weight of polymer and transition metal salt, the addition of transition metal salt is 0.0001～5%;
Said polymer is selected from cellulose, polyacrylonitrile, pitch or phenolic resins;
The preparation method's of the carbon absorbent for removing aldehyde of carried metal of the present invention two comprises the steps:
Transition metal salt solution is mixed with the monomer solution of polymer, adopt method in-situ polymerization well known in the art, dustless spinning, pre-oxidation, charing and activation then, make the carbon absorbent of carried metal;
Said transition metal salt is selected from sulfate, nitrate, acetate or the halide of transition metal;
Preferably cross slaine and be selected from copper, iron, cobalt, nickel or manganese;
The weight concentration of transition metal salt solution is 0.001%-10%;
The monomer of said polymer is selected from the monomer of cellulose, polyacrylonitrile, pitch or phenolic resins, and in the gross weight of polymer and transition metal salt, the addition of transition metal salt is 0.0001～5%.
The present invention has the following advantages:
(1) transition metal salt is dispersed in the surface or body of carbon absorbent.
(2) product that makes is pollution-free.
(3) full gear speed height, capacity are big, effective.
The specific embodiment
Embodiment 1
CuSO with 0.001%
4Solution 5ml joins in the 100ml cellulose, by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous loaded Cu.
The process conditions of dustless spinning, pre-oxidation, charing, activation and operating procedure be [He Fu, Wang Maozhang, carbon fiber and composite thereof in the literature.Science Press, Beijing, 1997.] in disclosed report has been arranged, detailed process is as follows:
With the filtration of spinning solution process with in the clean room spinning; make the high purity cellulose precursor, in 250 ℃ air dielectric, make preoxided thread then by pre-oxidation furnace pre-oxidation certain hour; under nitrogen protection, enter retort then, make the charcoal fiber 1150 ℃ of following charings.The charcoal fiber is fed activator activation certain hour under 800 ℃ of temperature, make NACF.Also charing and activation can be combined and carry out.
Performance test: at room temperature handle aldehyde-containing gas with this material of 1g, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 10ppm (nitrogen+air+formaldehyde+water vapour), flow is 10ml/min, time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 10mins, formaldehyde 0.5 hour.
Embodiment 2
FeCl with 0.1%
3Solution 5ml joins in the 100ml polyacrylonitrile solution, and stirring, ultrasonic dispersion are uniformly dispersed them then, through dustless spinning, pre-oxidation, charing, activation, makes the polyacrylonitrile active carbon fiber of load Fe.
The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: at room temperature handle aldehyde-containing gas with this material of 3g, formaldehyde entrance concentration 10ppm, the gas of steam entry concentration 100ppm (nitrogen+air+formaldehyde+water vapour).(flow is 12ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 15mins, formaldehyde 1.1 hours.
Embodiment 3
NiCl with 1%
2Solution 5ml joins in the 100ml pitch, by stir, ultrasonic dispersion, they are uniformly dispersed, through thermal polycondensation, heat from hydrogenation handle, solvent extraction, dustless then spinning, pre-oxidation, charing, activation make the asphalt based active carbon fiber of load Ni.
The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: at room temperature handle aldehyde-containing gas with this material of 0.5g, formaldehyde entrance concentration 15ppm, the gas of steam entry concentration 150ppm (nitrogen+air+formaldehyde+water vapour).(flow is 15ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 10mins, formaldehyde 3 hours.
Embodiment 4
CoCl with 2%
2Solution joins in the 100ml phenolic resins, through stirring, ultrasonic dispersion, make their even mixing, dustless then spinning, pre-oxidation, charing, activation make the phenolic resin based activated carbon fiber of load C o.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 25ppm (nitrogen+air+formaldehyde+water vapour) down at 50 ℃ with this material of 1g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 16mins, formaldehyde 4 hours.
Embodiment 5
NiCl with 2%
2Solution evenly mixes with 100ml acrylonitrile (AN), comonomer (methacrylic acid), initator (organic peroxide class), solvent (sodium sulfocyanate) etc., purifying, fully washing then, through over-churning or ammonification, dustless spinning, pre-oxidation, charing, activation, make the polyacrylonitrile active carbon fiber of load Ni.The effect of esterification or ammonification is: the cyclisation effect that prevents polymer in the preoxidation process significantly or introduce metal impurities does not often adopt methylene succinic acid isopropyl ester, metering system tert-butyl acrylate or the styrene sulphonic acid ester is improved the initiation effect of cyclisation as comonomer; Perhaps the copolymerization essence that contains carboxyl is carried out ammonification and handle, also can avoid introducing impurity.
The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 1ppm, the gas of steam entry concentration 25ppm (nitrogen+air+formaldehyde+water vapour) down at 80 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 26mins, formaldehyde 10 hours.
Embodiment 6
MnCl with 0.5%
2Solution joins in the 100ml cellulose (pulp), by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous load Mn.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 20ppm (nitrogen+air+formaldehyde+water vapour) down at 100 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 5mins, formaldehyde 3.2 hours.
Embodiment 7
NiCl with 1%
2Solution 5ml joins in the 100ml cellulose, by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous load Ni.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 20ppm (nitrogen+air+formaldehyde+water vapour) down at 100 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 16mins, formaldehyde 4 hours.
Embodiment 8
NiCl with 5%
2Solution joins in the 100ml cellulose, by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous load Mn.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 20ppm (nitrogen+air+formaldehyde+water vapour) down at 100 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 3.5mins, formaldehyde 4 hours.
Embodiment 9
NiCl with 8%
2Solution joins in the 100ml cellulose, by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous load Mn.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 20ppm (nitrogen+air+formaldehyde+water vapour) down at 100 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 6mins, formaldehyde 3 hours.
Embodiment 10
NiCl with 10%
2Solution joins in the 100ml cellulose, by stirring, ultrasonic dispersion, they is uniformly dispersed, and passes through dustless spinning, pre-oxidation, charing, activation then, makes the viscose-based active carbon fiber of fibrous load Mn.The process of dustless spinning, pre-oxidation, charing, activation is identical with embodiment 1.
Performance test: handle aldehyde-containing gas, formaldehyde entrance concentration 5ppm, the gas of steam entry concentration 20ppm (nitrogen+air+formaldehyde+water vapour) down at 100 ℃ with this material of 0.5g.(flow is 30ml/min), time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 4mins, formaldehyde 2 hours.
Comparative Examples 1
Adopt former state NACF (the BET specific area 750m identical with embodiment 3
2/ g), performance test is with embodiment 3, and time of break-through (being time of break-through when exit concentration is entrance concentration 5%) is respectively water vapour 5min, formaldehyde 60min.
From above comparing result as can be known, by in polymer solution, adding the transition metal salt of debita spissitudo, because transition metal salt can evenly mix with polymer solution, the adsorptive selectivity of the NACF sample PARA FORMALDEHYDE PRILLS(91,95) of prepared carried metal and adsorption capacity are owing to the catalyzed conversion effect of the metal pair formaldehyde of institute's load increases substantially.The concentration of used transition metal salt is effective in 0.1%～5% full gear.
Claims (8)
1. the carbon absorbent for removing aldehyde of a carried metal is characterized in that, is a kind of fibrous composition, and its component and weight percent content are:
Polymer 95～99.9999%
Transition metal 0.0001～5%.
2. the carbon absorbent for removing aldehyde of carried metal according to claim 1 is characterized in that, said high molecular polymer is selected from cellulose, polyacrylonitrile, pitch or phenolic resins.
3. the carbon absorbent for removing aldehyde of carried metal according to claim 1 is characterized in that, transition metal is selected from copper, iron, cobalt, nickel or manganese.
4. the method for preparing the carbon absorbent for removing aldehyde of each described carried metal of claim 1～3, it is characterized in that, comprise the steps: transition metal salt solution is mixed with polymer solution, dustless then spinning, pre-oxidation, charing, activation, make the carbon absorbent of carried metal, said polymer is selected from cellulose, polyacrylonitrile, pitch or phenolic resins, and in the gross weight of polymer and transition metal salt, the addition of transition metal salt is 0.0001～5%.
5. method according to claim 5, it is characterized in that, said transition metal salt is selected from sulfate, nitrate, acetate or the halide of transition metal, and transition metal salt is selected from copper, iron, cobalt, nickel or manganese, and the weight concentration of transition metal salt solution is 0.001%-10%.
6. the method for preparing the carbon absorbent for removing aldehyde of each described carried metal of claim 1～4, it is characterized in that, comprise the steps: transition metal salt solution is mixed with the monomer solution of polymer, in-situ polymerization, dustless spinning, pre-oxidation, charing and activation then makes the carbon absorbent of carried metal; The monomer of said polymer is selected from the monomer of cellulose, polyacrylonitrile, pitch or phenolic resins; In the gross weight of polymer and transition metal salt, the addition of transition metal salt is 0.0001～1%.
7. method according to claim 6 is characterized in that, said transition metal salt is selected from sulfate, nitrate, acetate or the halide of transition metal.
8. method according to claim 6 is characterized in that transition metal salt is selected from copper, iron, cobalt, nickel or manganese, and the weight concentration of transition metal salt solution is 0.001%-10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410068068 CN1631514A (en) | 2004-11-11 | 2004-11-11 | Metal supporting carbon absorbent for removing aldehyde and its preparing process |
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|---|---|---|---|
| CN 200410068068 CN1631514A (en) | 2004-11-11 | 2004-11-11 | Metal supporting carbon absorbent for removing aldehyde and its preparing process |
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| CN1631514A true CN1631514A (en) | 2005-06-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823767A (en) * | 2017-02-17 | 2017-06-13 | 广东美的环境电器制造有限公司 | Except the manufacture method of aldehyde material, except aldehyde material and filter |
| CN107398172A (en) * | 2017-08-08 | 2017-11-28 | 王婧宁 | It is a kind of efficiently to remove formaldehyde air purifying preparation |
| CN112827480A (en) * | 2021-01-08 | 2021-05-25 | 湖南大学 | Preparation method and application of antibiotic rapid adsorbent |
-
2004
- 2004-11-11 CN CN 200410068068 patent/CN1631514A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823767A (en) * | 2017-02-17 | 2017-06-13 | 广东美的环境电器制造有限公司 | Except the manufacture method of aldehyde material, except aldehyde material and filter |
| CN107398172A (en) * | 2017-08-08 | 2017-11-28 | 王婧宁 | It is a kind of efficiently to remove formaldehyde air purifying preparation |
| CN112827480A (en) * | 2021-01-08 | 2021-05-25 | 湖南大学 | Preparation method and application of antibiotic rapid adsorbent |
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