CN109731558A - A kind of anion activity carbon nanometer composite material and the preparation method and application thereof - Google Patents
A kind of anion activity carbon nanometer composite material and the preparation method and application thereof Download PDFInfo
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- CN109731558A CN109731558A CN201910141845.5A CN201910141845A CN109731558A CN 109731558 A CN109731558 A CN 109731558A CN 201910141845 A CN201910141845 A CN 201910141845A CN 109731558 A CN109731558 A CN 109731558A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of anion activity carbon nanometer composite materials and the preparation method and application thereof.The preparation method mainly includes sequentially adding active carbon nanoparticles, negative ion powder, distilled water and acrylic acid, after mixing evenly reaction a period of time；It is passed through nitrogen, initiator and crosslinking agent reaction is added；It is filtered, is washed, drying obtains nanocomposite.The present invention adds negative ion powder by the method for chemical modification in active carbon, the nanocomposite of preparation is set constantly to release the negative oxygen ion being beneficial to health, the absorption and decomposability to the volatile organic matter in air such as formaldehyde, toluene, benzene etc. are enhanced simultaneously, the adsorbent that can be used as the pollutants such as removal indoor formaldehyde, has a good application prospect.
Description
Technical field
The invention mainly relates to a kind of chemical modification modes of active carbon, and in particular to a kind of anion active carbon nanometer is multiple
Condensation material and the preparation method and application thereof.
Background technique
Formaldehyde (HCHO) is commonly called as formalin, and the effumability liquid with penetrating odor, formalin often does anti-corrosion
Agent and fungicide.Formaldehyde source is wide, toxicity is big, the duration is long, is one of the main reason for causing indoor pollution.Concentration of formaldehyde
It is excessively high the irritating effect of human skin mucous membrane to be chronically under the formaldehyde environment of low concentration, be will also result in human health
It influences.The pollution of formaldehyde is mainly derived from wood-based plate, coating, foamed plastics of interior decoration etc. in life, and one side formaldehyde is
The main binder for producing wood-based plate, can evaporate into air, cause indoor pollution；On the other hand, the hemicellulose in timber
Hydrolysis can also release a small amount of formaldehyde.
The method removed in formaldehyde room at present is mainly include the following types: feeling deodorizing method, mainly passes through air freshener etc.
Product with intense flavors covers the penetrating odors of the escaping gas such as formaldehyde, the solution first that this method could not be basic
The problem of aldehyde pollutes；Ventilation method mainly passes through the air constantly flowed, improves indoor air quality, and it is dense to reduce formaldehyde
Degree；Physisorphtion generally refers to be adsorbed using the active carbon sold on the market.Active carbon has good hole knot
Structure and relatively large specific surface area, can effectively formaldehyde adsorption.But the active carbon due to selling on the market have ash content and
The adsorption capacity of impurity, PARA FORMALDEHYDE PRILLS(91,95) is poor, and adsorption rate is slow, and easily causes secondary pollution, so generally using physics or change
Method is modified, and improves absorption property and power of regeneration；Chemiadsorption refers to molecule, atom, atomic group of absorption etc.
It is be combined with each other by the atom or ion of chemical bond and adsorbent surface, there is selectivity and high efficiency, chemical reagent is sprayed
Chemical reaction can occur with the formaldehyde of family into air and achieve the purpose that removing, but since the release process of formaldehyde is slow
It is slow and lasting, the sprinkling and reaction of chemical reagent be moment complete, so effect it is not satisfactory and removal gas compare
It is single.
The main component of negative ion powder is the mixture of ultra-fine tourmaline and ceramics, is had the characteristics that natural, non-toxic and tasteless.
Negative ion powder can convey negative oxygen ion to dust, bacterium and smog etc. in air, and charge, which combines, can generate coagulation, reach
To the effect of purification air.Anion main effect in life, which has, eliminates peculiar smell and pernicious gas, health-care effect and Shui Chu
Reason etc., the concentration of anion is to measure one of the factor of air quality in air, and efficient anion can be generated now by developing
Interior wall functional paint and the finishing materials such as paint, while tourmaline, negative ion powder and negative ion paint also have antibacterial action, suppression
The growth of bacterium processed is conducive to purify air.
Currently, have multiple patents in terms of related negative ion powder modified activated carbon, as CN106752154A,
CN105481045A,CN104324692A.Such as patent CN106752154A, by active carbon and negative ion powder, water, auxiliary agent, defoaming
Agent, plant additive etc. carry out certain proportion weight number and are mixed, and it is net that the modified activated carbon prepared can be added to air
Change in coating, the harmful substance in air can be adsorbed, while releasing negative oxygen ion, be conducive to human health.But the patent
It is using physical mixing processes, active carbon be easy to cause secondary pollution to the limited sorption capacity of harmful substance.Patent
CN105481045A is obtained only using active carbon, anion composite powder, polyethylene, sodium metasilicate by high temperature sintering after compression moulding
Water material for core, can discharge anion and far infrared radiation, and Magnetized water molecules accelerate the electron transmission of organism.Patent
CN104324692A is modified active carbon by surfactant, while loading formaldehyde catching agent, modified active obtained
Charcoal can adsorb and decomposing formaldehyde, does not easily cause secondary pollution, but the capture dosage of infusion process load is lower.
Summary of the invention
The purpose of the present invention is to provide a kind of anion activity carbon nanometer composite materials and the preparation method and application thereof.This
Present invention is simple, and used raw material is environmentally protective, can be widely applied to industrial production.The nano combined material of preparation
Material can be adsorbed effectively with volatile organic matters such as decomposing formaldehydes, have good power of regeneration, while can be added to painting
Functional product is prepared in material, health treatment.
A kind of preparation method of anion activity carbon nanometer composite material of the invention, comprising the following steps:
(1) weigh active carbon nanoparticles and negative ion powder, measure distilled water and acrylic acid, after mixing temperature be 60~
80 DEG C are 1~2h of polymerization reaction under conditions of 200~400r/min with mixing speed；
(2) initiator is added in the solution into step (1) after reaction, is continually fed into 15~30min of nitrogen；
(3) by step (2) resulting mixed solution, 4~6h is stirred to react at 80~100 DEG C of temperature；
(4) crosslinking agent is added into the solution after reaction in step (3), it is stirred to react 10 at 40~60 DEG C of temperature~
16h；
(5) solution after reaction in step (4) is filtered, is washed with distilled water to neutrality, unreacted crosslinking agent is washed
It washs completely, obtained solid is dried at 60~80 DEG C, be ground to powdery to get anion activity carbon nanometer composite material is arrived.
Further, each raw material composition is as follows in the preparation method: 75~85.6wt% of distilled water, active carbon nanoparticles 5
~15wt%, 5~10wt% of negative ion powder, 1~3wt% of acrylic acid, initiator be 0.4~1wt%, crosslinking agent be 0.1~
2wt%, active carbon nanoparticles and negative ion powder mass ratio are 1:1~3:1, and preferably active carbon nanoparticles and negative ion powder mass ratio are 3:
1。
In the step (1), mixing speed can be 200r/min, 300r/min, 400r/min, but be not limited only to enumerate
Data, be that other data for enumerating are equally applicable in above range.
In the step (2), the time that is continually fed into of nitrogen is 15min, 20min, 30min, but be not limited only to enumerate
Data are that other data for enumerating are equally applicable in above range.
In the step (3), initiator be potassium peroxydisulfate or ammonium persulfate, mass percent 0.4wt%, 0.8wt%,
1.0wt%, but be not limited only to the data enumerated is that other data for enumerating are equally applicable in above range；Reaction time is
4h, 5h, 6h, but be not limited only to the data enumerated are that other data for enumerating are equally applicable in above range.
In the step (4), crosslinking agent be one of glutaraldehyde, N-N- methylene-bisacrylamide, glyoxal or
A variety of, parts by weight can be 0.1wt%, 0.5wt%, 1wt%, 2wt%, but be not limited only to the data enumerated, in above range
It is that other data for enumerating are equally applicable；Reaction time can be 10h, 12h, 14h, 16h, but be not limited only to the number enumerated
According to being that other data for enumerating are equally applicable in above range.
Anion activity carbon nanometer composite material produced by the present invention can removal in volatile organic matter, heavy metal wastewater thereby
It is applied in processing.
Specifically, anion activity carbon nanometer composite material prepared by the present invention can adsorb and decompose volatility in air
Organic matter such as formaldehyde etc., while negative oxygen ion lasting can be released, air is purified, and can be also used for heavy metal wastewater thereby
Processing；It can not only use, can simultaneously serve as the raw material of other products such as coating, health treatment and add separately as adsorbent
Add agent, there is vast application prospect.
Beneficial effects of the present invention: remove on the market now formaldehyde active carbon mainly takes is physical adsorption process,
Utilization rate is low and effect is poor, and be easy to cause secondary pollution.Compare normal activated carbon, negative ion powder that the present invention uses and
Active carbon nanoparticles have granularity small, and flourishing surface pore structure and high specific surface area, adsorption capacity is strong, passing through of the present invention
Method is modified, and using acrylic acid as function monomer, polymerization reaction first occurs with active carbon and negative ion powder, initiator is added
Free radical is formed, can preferably be grafted, a certain amount of crosslinking agent is then added and is crosslinked, increase the ratio of active carbon
Surface area increases the oxygen-containing functional group of activated carbon surface, not only can be with organic molecules such as formaldehyde adsorptions, while can be absorption
Organic molecule be decomposed into small molecule, while releasing the anion beneficial to human body；Negative ion powder is given by conveying negative electricity
Dust, smog in air etc. have the function that purify air to realize coagulation.
Anion activity carbon nanometer composite material prepared by the present invention mainly has the advantage that nanometer prepared by the present invention is multiple
Condensation material can adsorb volatile organic matter, such as formaldehyde, benzene, toluene, ammonia, PM2.5, and the efficiency of formaldehyde adsorption is up to 88%~
99%, it can simultaneously serve as the raw materials such as coating, paint, be with a wide range of applications.Materials safety, it is at low cost；Preparation method
Simply, operating condition is easy to control, can expand for industrial production；The effect safety and stability of formaldehyde is removed, it can be repeatedly sharp
With removing the high-efficient of formaldehyde；The anion beneficial to human body is discharged, air quality is purified.
Specific embodiment
Technical solution of the present invention is further described below with reference to specific embodiment, works as embodiment of the present invention
It is not limited only to this, data collocation within the above range is applicable in.
The measurement method of the removal rate r of composite material PARA FORMALDEHYDE PRILLS(91,95) obtained by following embodiments is as follows: weighing composite wood described in 2g
Material is laid in surface plate, and concentration of formaldehyde is adjusted in closed container in 1~2mg/m3, surface plate is placed in closed container
Start timing, at regular intervals interval record concentration of formaldehyde, stops until concentration of formaldehyde stablizes constant in closed container real
It tests, experiment is repeated several times and is averaged.Calculate the removal rate of formaldehyde: r=(c0-ce)/c0× 100%, wherein c0And ceRespectively
Concentration of formaldehyde (mg/m when absorption is preceding and reaches adsorption equilibrium3)。
Embodiment 1
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
5wt%, negative ion powder 5wt%, distilled water 85.6wt%, acrylic acid 3wt%, potassium peroxydisulfate 0.4wt%, glutaraldehyde 1wt%.
Active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned mass percent are sequentially added, mixing speed is set as 200r/min,
It is uniformly mixed and is placed in thermostat water bath, the temperature of regulating thermostatic water-bath is polymerization reaction 2h under conditions of 60 DEG C；It is added
The initiator of specified quality, is then passed through nitrogen 15min, reacts 4h under conditions of temperature is 80 DEG C；Crosslinking agent is added, in temperature
Degree is set as reacting 14h at 40 DEG C；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, by unreacted
Crosslinking agent washes clean, by obtained solid 60 DEG C dry, be ground to powdery, obtain composite material, measure its PARA FORMALDEHYDE PRILLS(91,95)
Adsorption effect obtain the removal rate of formaldehyde.
Embodiment 2
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
10wt%, negative ion powder 10wt%, distilled water 76.1wt%, acrylic acid 3wt%, potassium peroxydisulfate 0.8wt%, glutaraldehyde
0.1wt%.Active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned weight ratio are sequentially added, mixing speed is set as
200r/min is uniformly mixed and is placed in thermostat water bath, and the temperature of regulating thermostatic water-bath reacts 1h under conditions of being 60 DEG C；
The initiator of specified quality is added, is then passed through nitrogen 20min, 4h is reacted under conditions of temperature is 80 DEG C, crosslinking agent is added,
It is 40 DEG C of reaction 16h in temperature setting；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, it will be not anti-
Obtained solid is dried at 60 DEG C, is ground to powdery, finally obtains composite material, measure it by the crosslinking agent washes clean answered
The adsorption effect of PARA FORMALDEHYDE PRILLS(91,95) obtains the removal rate of formaldehyde.
Experimental example 3
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
15wt%, negative ion powder 5wt%, distilled water 76.7wt%, acrylic acid 2wt%, potassium peroxydisulfate 0.8wt%, glutaraldehyde
0.5wt.Active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned weight ratio are sequentially added, mixing speed is set as 250r/
Min is uniformly mixed and is placed in thermostat water bath, and the temperature of regulating thermostatic water-bath reacts 1h under conditions of being 60 DEG C；It is added
The initiator of specified quality, is then passed through nitrogen 20min, and 4h is reacted under conditions of temperature is 80 DEG C, crosslinking agent is added, in temperature
Degree is set as 40 DEG C of reaction 12h；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, it will be unreacted
Obtained solid is dried at 60 DEG C, is ground to powdery, finally obtains composite material, measure it to first by crosslinking agent washes clean
The adsorption effect of aldehyde obtains the removal rate of formaldehyde.
Embodiment 4
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
15wt%, negative ion powder 5wt%, distilled water 76.2wt%, acrylic acid 2wt%, ammonium persulfate 0.8wt%, glutaraldehyde
1wt%.Active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned weight ratio are sequentially added, mixing speed is set as 300r/
Min is uniformly mixed and is placed in thermostat water bath, and the temperature of regulating thermostatic water-bath reacts 1h under conditions of being 60 DEG C；It is added
The initiator of specified quality, is then passed through nitrogen 30min, and 4h is reacted under conditions of temperature is 80 DEG C, crosslinking agent is added, in temperature
Degree is set as 40 DEG C of reaction 12h；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, it will be unreacted
Obtained solid is dried at 60 DEG C, is ground to powdery, finally obtains composite material, measure it to first by crosslinking agent washes clean
The adsorption effect of aldehyde obtains the removal rate of formaldehyde.
Experimental example 5
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
15wt%, negative ion powder 5wt%, distilled water 75.2wt%, acrylic acid 2wt%, ammonium persulfate 0.8wt%, glutaraldehyde
2wt%.Active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned weight ratio are sequentially added, mixing speed is set as 300r/
Min is uniformly mixed and is placed in thermostat water bath, and the temperature of regulating thermostatic water-bath reacts 1h under conditions of being 60 DEG C；Then
It is passed through nitrogen 30min, the initiator that specified quality is added reacts 4h under conditions of temperature is 80 DEG C, crosslinking agent is added, in temperature
Degree is set as 40 DEG C of reaction 12h；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, it will be unreacted
Obtained solid is dried at 60 DEG C, is ground to powdery, finally obtains composite material, measure it to first by crosslinking agent washes clean
The adsorption effect of aldehyde obtains the removal rate of formaldehyde.
Experimental example 6
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
15wt%, negative ion powder 5wt%, distilled water 75wt%, acrylic acid 3wt%, potassium peroxydisulfate 1wt%, N-N- di-2-ethylhexylphosphine oxide third
Acrylamide 1wt%.Sequentially add active carbon, negative ion powder, distilled water, the acrylic acid of aforementioned weight ratio, mixing speed setting
It for 400r/min, is uniformly mixed and is placed in thermostat water bath, the temperature of regulating thermostatic water-bath is reacted under conditions of being 80 DEG C
2h；The initiator of specified quality is added, is then passed through nitrogen 30min, 6h is reacted under conditions of temperature is 100 DEG C, is added and hands over
Join agent, is 60 DEG C of reaction 10h in temperature；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, it will be not anti-
Obtained solid is dried at 80 DEG C, is ground to powdery, finally obtains composite material, measure it by the crosslinking agent washes clean answered
The adsorption effect of PARA FORMALDEHYDE PRILLS(91,95) obtains the removal rate of formaldehyde.
Embodiment 7
Each raw material is weighed or is measured according to following mass percent in the preparation of composite material: active carbon nanoparticles
15wt%, negative ion powder 5wt%, distilled water 75wt%, acrylic acid 3wt%, ammonium persulfate 1wt%, glyoxal 1wt%.According to
Secondary active carbon, negative ion powder, distilled water, the acrylic acid that aforementioned weight ratio is added, mixing speed are set as 400r/min, mix
It is uniformly placed in thermostat water bath, the temperature of regulating thermostatic water-bath reacts 2h under conditions of being 80 DEG C；Specified quality is added
Initiator, be then passed through nitrogen 15min, react 6h under conditions of temperature is 100 DEG C, crosslinking agent is added, be 60 in temperature
DEG C reaction 10h；Mixed solution after reaction is filtered, is washed with distilled water to neutrality, unreacted crosslinking agent is washed
Completely, obtained solid is dried at 80 DEG C, is ground to powdery, finally obtains composite material, measure the absorption effect of its PARA FORMALDEHYDE PRILLS(91,95)
Fruit obtains the removal rate of formaldehyde.
Experimental example 8
After anion activity carbon nanometer composite material formaldehyde adsorption reaches saturated extent of adsorption in Example 3, at 80 DEG C
Dry 10h is desorbed in drying box, and the formaldehyde removal rate of second adsorption is 90%, repeats above step, and active carbon is inhaled three times
Attached formaldehyde removal rate 87%, four formaldehyde adsorption removal rates of active carbon are 84%, and the removal rate of five formaldehyde adsorptions is 80%, are said
The repeated removal rate of the bright anion activity carbon nanometer composite material PARA FORMALDEHYDE PRILLS(91,95) can reach 80% or more, have good suction
Attached performance and reusing.
Take raw material nano active carbon carry out formaldehyde adsorption experiment test, be labeled as raw material 1, take raw material negative ion powder into
The experiment of row formaldehyde adsorption is tested, and raw material 2 are labeled as.
Test result is as follows for embodiment 1-7 and raw material shown in table 1:
1 formaldehyde removal rate test data table of table
| Project | Formaldehyde removal rate |
| Raw material 1 | 86% |
| Raw material 2 | 76% |
| Embodiment 1 | 88% |
| Embodiment 2 | 89.8% |
| Embodiment 3 | 96% |
| Embodiment 4 | 98% |
| Embodiment 5 | 92% |
| Embodiment 6 | 90.3% |
| Experimental example 7 | 91.2% |
As can be known from Table 1, it is handled and the active carbon nanoparticles after cross-linking agents, the energy of formaldehyde adsorption by acrylic acid
Power significantly improves；Acrylic acid is function monomer, and the oxygen-containing group in its surface can be increased by introducing on active carbon, enhances PARA FORMALDEHYDE PRILLS(91,95)
Absorption property.Initiator can effectively cause monomer and carry out polymerization reaction；Glutaraldehyde is a kind of best crosslinking agent of effect, but
It needs to control dosage of crosslinking agent, if excessively will lead to crosslinking is excessively formed the big activated carbon microballon of particle, is unfavorable for adsorbing；This hair
The anion activity carbon nanometer composite material of bright preparation can release negative oxygen ion, can agglomerate with the harmful substance in air
Coagulation improves indoor air quality to play the role of purifying air.
The particular technique feature described in above-mentioned specific embodiment can pass through any other suitable mode
It is combined, the present invention does not explain separately herein.
Above specific embodiment is only the preferred embodiment of the present invention, is not intended to restrict the invention, all according to this
The technical spirit of invention any simple modification, equivalent variations and modification made to the above embodiment, each fall within the technology of the present invention
In the protection scope of scheme.
Claims (6)
1. a kind of preparation method of anion activity carbon nanometer composite material, it is characterised in that according to the following steps:
(1) active carbon nanoparticles and negative ion powder are weighed, distilled water and acrylic acid are measured, are after mixing 60~80 in temperature
DEG C, mixing speed be 200~400 r/min under conditions of 1~2 h of polymerization reaction；
(2) initiator is added in the solution into step (1) after reaction, is continually fed into 15~30 min of nitrogen；
(3) step (2) resulting mixed solution is stirred to react 4~6h at 80~100 DEG C of temperature；
(4) crosslinking agent is added in the solution into step (3) after reaction, is stirred to react 10~16 h at 40~60 DEG C of temperature；
(5) solution after reaction in step (4) is filtered, is washed with distilled water to neutrality, unreacted crosslinking agent washed dry
Only, obtained solid is dried at 60~80 DEG C, is ground to powdery to get anion activity carbon nanometer composite material is arrived.
2. preparation method according to claim 1, it is characterised in that: each raw material composition is as follows in the preparation method: distillation
75~85.6wt% of water, 5~15wt% of active carbon nanoparticles, 5~10wt% of negative ion powder, 1~3wt% of acrylic acid, initiator be 0.4~
1wt%, crosslinking agent is 0.1~2wt%, and the mass ratio of active carbon nanoparticles and negative ion powder is 1:1~3:1.
3. preparation method according to claim 1, it is characterised in that: initiator is potassium peroxydisulfate or mistake in the step (2)
Ammonium sulfate.
4. preparation method according to claim 1, it is characterised in that: crosslinking agent is glutaraldehyde, the Asia N-N- in the step (4)
One of bisacrylamide, glyoxal etc. are two or more.
5. the anion activity carbon nanometer composite material that any one of the claim 1-4 preparation method is prepared.
6. anion activity carbon nanometer composite material is at the removal of volatile organic matter, heavy metal wastewater thereby described in claim 6
Application in reason.
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Application publication date: 20190510 |
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