CN107469467A - A kind of preparation method of efficient gas absorbent-type air filting material - Google Patents
A kind of preparation method of efficient gas absorbent-type air filting material Download PDFInfo
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- CN107469467A CN107469467A CN201710860392.2A CN201710860392A CN107469467A CN 107469467 A CN107469467 A CN 107469467A CN 201710860392 A CN201710860392 A CN 201710860392A CN 107469467 A CN107469467 A CN 107469467A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1615—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of natural origin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0032—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions using electrostatic forces to remove particles, e.g. electret filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
Abstract
The invention discloses a kind of efficient gas absorbent-type air filting material preparation method, string is discongested, fibrillation handles to obtain fibrous suspension I；Zinc nitrate hexahydrate is dissolved under room temperature condition and obtains solution A, then 2 methylimidazoles are dissolved into acquisition solution B respectively；First solution A is poured into fibrous suspension I and is stirred continuously, is configured to fibrous suspension II；Solution B is poured into fibrous suspension II again and stirs lasting stirring, finally obtains milky suspension II I.24~48h of reaction in the oil bath environment for be placed in 60~75 DEG C is poured into tetrafluoroethene reactor again, and after reaction terminates, the load crystal fibres of ZIF 8 are isolated by vacuum filtration method；And it is configured to fiber dilution liquid, fiber dilution liquid is put into shaping vessel and carries out freeze forming, then freeze-drying process is carried out, obtains the environment-friendly type air filtering material with high efficiency of additive capability, the preparation method simple possible has good development prospect.
Description
Technical field
The invention belongs to filtering adsorbing material technical field, and in particular to a kind of efficient gas absorbent-type air filting material
Preparation method.
Background technology
The quickening of aggravation and process of industrialization recently as mankind's activity, atmosphere pollution become further serious, and
The constituent component of atmosphere pollution also becomes more sophisticated.In atmosphere pollution, except the particle for enjoying the mankind to pay close attention at present
Thing (PM) pollution is outer, and some toxic gases and the exceeded of volatile organic matter concentration can also give mankind's health care belt to carry out great prestige
The side of body.Wherein formaldehyde can not only have an impact to the nervous system of the mankind as a kind of typical dusty gas, cause retinopathy
Become and the symptom such as apoplexy, Long Term Contact can cause the incidence of disease of cancer to improve 1.6 times in addition, and its toxic action can be to the life of people
Had a strong impact on health generation.
Nowadays, solving the problems, such as to adsorb toxic gas and Cleaning Air turns into urgently to be resolved hurrily difficult miscellaneous after industrialization polluted
Disease.At present, largely research all concentrates on using activated carbon granule thing, active carbon fibre relevant gas absorption type air filting material
The high-precision electrostatic spinning technique of peacekeeping carries out adsorption treatment to toxic gas, but has that adsorption effect is poor, filter efficiency is low
The problems such as.Be distributed in by the method for conveying spheric granules activated carbon using air-flow in macromolecular fibre micropore, then with nonwoven
Cloth base material hot pressing is compounded to form the filtering material of adsorbable purification, and it is straight that this material compared to activated carbon granule thing is distributed in non-woven fabrics
Connect hot-forming or through adhesive curing molding filtering material reduce activated carbon drop, skewness the problems such as, but its give birth to
Production. art is complicated, is unsuitable for large-scale industrial production (application number：CN200510024848.9)；Utilize electrostatic spinning technique
Using chliorinated polyvinyl chloride, diacetate fiber and polyether sulfone as raw material, the composite adsorption mistake with gradient filtration precision is prepared
Filter material material, and have the characteristics that light, dust containing capacity is high, but its removal efficiency to 0.5~0.6 μm of particulate is only 80~99%
(application number：CN200520118597.6)；NACF is used to form height for electrode adsorption material and cylindrical conductor mandrel
The adsorption filtration device of effect, device simple possible, the convenient disassembly, but it is primarily adapted for use in the water body processing (application number of pollution：
CN201510593323.0)；Metal organic framework (MOFs) material, it is organic by transition metal particles and oxygen-containing/nitrogen as one kind
The multidimensional framework material that part is formed by connecting, there is porosity height, bore hole size is controllable, specific surface area is big, structurally ordered, preparation
The features such as simple so that it has wide answer in the field such as gas absorption and separation, catalysis, drug delivery, chemical sensor
Use prospect.Under high-temperature and high-pressure conditions so that organometallic skeletal compound growth is organic so as to obtain metal in nickel substrate
Skeleton film, it has preferable separating effect (application number to hydrogen/carbon dioxide：CN201510444805.X).It is above-mentioned listed
Patent and other same domain patents major part prepare gas absorption type using addition activated carbon granule or NACF
Air filting material, but problems such as generally existing adsorption effect is poor, filter efficiency is low.And use and add metal organic framework
(MOFs) prepared on the premise of with compared with air filting material of high absorption property etc. not correlative study at present.
The content of the invention
It is existing to overcome it is an object of the invention to provide a kind of preparation method of efficient gas absorbent-type air filting material
The problem of with the presence of technology, the present invention using hydro-thermal method by ZIF-8 nanocrystal growths on fibrillated cellulose fibers surface, with
The cellulose fibre of ZIF-8 crystal modification is obtained, recycles Freeze Drying Technique to prepare high adsorption air filtration material
Material.Because the specific surface area of ZIF-8 crystal is up to 956.1489m2/ g, the filtering material through the modification of ZIF-8 crystal is caused to compare table
Area is from 7.10m2/ g is increased to 614.01m2/ g, suction-operated of the filtering material to fine particle is improved, so as to improve it
Air filter efficiency.Further, since the introducing in structure with the ZIF-8 nanocrystals of open metallic site can improve fiber
The gas sorption ability of plain base air filter material.In addition, ZIF-8 has prominent " revolving door effect ", diameter can be adsorbed
The gas molecule bigger than its aperture, so as to further increase the filtering material through the modification of ZIF-8 nanocrystals to toxic gas
Adsorption capacity.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of preparation method of efficient gas absorbent-type air filting material, comprises the following steps：
Step 1：String is discongested, fibrillation processing, obtain finely dispersed fibrous suspension I；
Step 2：Zinc nitrate hexahydrate is dissolved in deionized water under room temperature condition, obtains solution A, then by 2- methyl
Imidazoles is dissolved separately in deionized water, obtains solution B；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it, utilizes six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, acquisition carry Zn2+Fibrous suspension II；
Step 4：After fibrous suspension II is stirred, solution B is poured into fibrous suspension II immediately, continued
Stirring, so as to obtain fibrous suspension III；
Step 5：Suspension II I is poured into ptfe autoclave, reacted in oil bath environment, reaction terminates
Afterwards, the fiber of load ZIF-8 crystal, and the fibre using deionized water to load ZIF-8 crystal are isolated by vacuum filtration method
Dimension cleaning is several times；
Step 6：The fiber for the load ZIF-8 crystal that step 5 obtains is configured to fiber dilution liquid, by fiber dilution liquid
It is put into shaping vessel and carries out freeze forming, obtains frozen samples；
Step 7：Frozen samples are subjected to freeze-drying process, remove ice crystal so as to obtain efficient gas absorbent-type air
Filtering material.
Further, step 1 is specifically that string pulpboard is soaked into 12~20h, discongests 12000~15000r,
Then defibrination process is carried out, defibrination revolution is 20000~50000r.
Further, fibrous suspension I mass concentration is 1.5~2.5% in step 1.
Further, the mass concentration of zinc nitrate hexahydrate is 8~13% in the solution A described in step 2.
Further, the mass concentration of 2-methylimidazole is 30~55% in the solution B described in step 2.
Further, the mass ratio of fibrous suspension I, solution A and solution B is (600~1000)：(10.04~
13.34)：(47.14~76.67).
Further, oil bath temperature is 60~75 DEG C in step 5, and the reaction time is 24~48h.
Further, the concentration of the fiber dilution liquid in step 6 is 1.5~2%.
Further, freeze forming condition is in step 6：Cryogenic temperature is -45~-56 DEG C, and cooling time is 3~6h.
Further, freeze-drying process condition is in step 7：Drying temperature is -45~-56 DEG C, drying time 48
~56h, the vacuum of drying process is 15~25Pa.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention recycles freeze-drying using the string of hydro-thermal method in-situ preparation ZIF-8 nanocrystals modification
Prepare green, degradable high adsorption air filting material.In ungroomed cellulose base air filting material
In the presence of substantial amounts of void network structure, ZIF-8 nanocrystals can be evenly distributed in filter material by in-situ synthesized, and
The method of absorption property is improved compared to activated carbon granule is attached into surface of filter medium using adhesive, in-situ synthesized is reduced
It is wrapped in the destruction of the ZIF-8 nanocrystal layers of fiber surface or comes off, it has successfully been retained in the filter material prepared
In material.The ZIF-8 nanocrystal layers of one side fiber surface parcel, make fiber surface become more coarse, when particulate matter and fibre
When dimension table face collides, contribute to crown_interception of the enhancing to particulate matter, while caused after the modification of ZIF-8 nanocrystals
The very fast increase of specific surface area of filter material material, improves the suction-operated to particulate matter, ultimately results in the rising of filter efficiency.It is another
Aspect, ZIF-8 nanocrystal surfaces can cause its positively charged without the defects of metallic site and ZIF-8 nanocrystals balanced
Lotus, so as to electronegative PM2.5 surfaces of polarizing, the electrostatic adsorption between filtering material and PM2.5 is improved, simultaneously
ZIF-8 crystal, the organometallic skeletal compound abundant as a kind of, pore structure bigger than surface is to volatile toxic gas
Have a good adsorption effect, thus the cellulose base air filting material after nanocrystal is modified to toxic gas (such as：
Formaldehyde etc.) there is good absorption property.
Compared to filtering materials such as polytetrafluoroethylene films, the plant cellulose base material that the present invention uses has green ring
The features such as protecting, be degradable and recyclable, and the string modified in addition using hydro-thermal method in-situ preparation ZIF-8 nanocrystals,
So that ZIF-8 nanocrystals are evenly distributed in fiber surface, while reduce coming off and destroying for ZIF-8 nanocrystals, then
The larger high adsorbability fiber element base air filter material of specific surface area is prepared using Freeze Drying Technique.It is of the invention a kind of high
Effect gas absorption type air filting material preparation method has the characteristics that technique is simple, convenient for production.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is that the SEM for the efficient gas absorbent-type air filting material that blank Example is prepared with the embodiment of the present invention 3 schemes
(a- blank Examples；B- embodiments 3；a:×2500；b:×2500).
Embodiment
Embodiments of the present invention are described in further detail below in conjunction with the accompanying drawings：
Referring to Fig. 1, a kind of preparation method of efficient gas absorbent-type air filting material, comprise the following steps：
Step 1：Take and soak 12~20h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer
Scattered fleeces 12000~15000r of aggressiveness, after the abundant swollen of fiber is discongested, then carries out fibrillation processing, defibrination revolution is
20000~50000r, then fibrillating fibre is diluted with water to be made into the fibrous suspension I that mass concentration is 1.5~2.5% standby
With；
Step 2：1.04~1.34g zinc nitrate hexahydrates are dissolved in 9~12g deionized waters under room temperature condition, obtained
The mass concentration of solution A, wherein zinc nitrate hexahydrate is 8~13%；17.14~36.67g2- methylimidazoles are dissolved respectively again
In 30~40g deionized waters, solution B is obtained, the wherein mass concentration of 2-methylimidazole is 30~55%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After 2~10min of fibrous suspension II mechanical agitations, solution B is poured into fibrous suspension II immediately
In, continue 2~10min of mechanical agitation, so as to obtain milky fibrous suspension III；
Step 5：Fibrous suspension III in step 4 is poured into ptfe autoclave, at 60~75 DEG C
24~48h is reacted in oil bath environment.After reaction terminates, the fiber of load ZIF-8 crystal, and profit are isolated by vacuum filtration method
It is cleaned for several times with deionized water, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that concentration is 1.5~2% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then takes fiber dilution liquid to pour into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -45~-56 DEG C to freeze temperature, and cooling time is 3~6h, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 15~25Pa, and built-in temperature is -45~-56 DEG C, and drying time is 48~56h, from
And obtain efficient gas absorbent-type air filting material.
The present invention is described in further detail with reference to embodiment：
Blank Example
Step 1：Take and soak 16h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 13500r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 35000r, then by original
It is that 1.8% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：The fibrous suspension I prepared in step 1 is poured into glass culture dish, is positioned over freeze drier
In, freeze forming condition is：Cryogenic temperature is -50 DEG C, cooling time 4.2h, so as to complete the preliminary freeze forming of sample；
Step 3：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 19Pa, and built-in temperature is -50 DEG C, drying time 51h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 1
Step 1：Take and soak 12h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 12000r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 20000r, then by original
It is that 1.5% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.04g zinc nitrate hexahydrates are dissolved in 12g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 8%；17.14g 2-methylimidazoles are dissolved separately in 40g deionized waters again, obtained
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 30%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 2min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 2min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 60 DEG C of oil bath environment
Middle reaction 24h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.5% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -45 DEG C, cooling time 3h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 15Pa, and built-in temperature is -45 DEG C, drying time 48h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 2
Step 1：Take and soak 14h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 13000r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 30000r, then by original
It is that 1.7% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.08g zinc nitrate hexahydrates are dissolved in 9.5g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 8.98%；18g 2-methylimidazoles are dissolved separately in 32g deionized waters again, obtained
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 36%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 3min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 3min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 62 DEG C of oil bath environment
Middle reaction 26h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.7% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -48 DEG C, cooling time 4h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 18Pa, and built-in temperature is -48 DEG C, drying time 50h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 3
Step 1：Take and soak 16h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 13500r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 35000r, then by original
It is that 1.8% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.10g zinc nitrate hexahydrates are dissolved in 10g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 10%；20g 2-methylimidazoles are dissolved separately in 34g deionized waters again, obtained
The mass concentration of solution B, wherein 2-methylimidazole is 37.04%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 5min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 5min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 63 DEG C of oil bath environment
Middle reaction 30h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.8% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -50 DEG C, cooling time 4.2h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 19Pa, and built-in temperature is -50 DEG C, drying time 51h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 4
Step 1：Take and soak 17h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 14000r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 38000r, then by original
It is that 1.9% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.12g zinc nitrate hexahydrates are dissolved in 10.5g deionized waters under room temperature condition, obtain solution A,
Wherein the mass concentration of zinc nitrate hexahydrate is 9.64%；23g 2-methylimidazoles are dissolved separately in 35g deionized waters again,
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 39.66%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 6min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 6min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 65 DEG C of oil bath environment
Middle reaction 30h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.9% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -52 DEG C, cooling time 4.5h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 20Pa, and built-in temperature is -52 DEG C, drying time 53h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 5
Step 1：Take and soak 18h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 14500r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 40000r, then by original
It is that 2.0% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.15g zinc nitrate hexahydrates are dissolved in 11g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 9.47%；27g 2-methylimidazoles are dissolved separately in 38g deionized waters again, obtained
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 42.54%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 8min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 7min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 67 DEG C of oil bath environment
Middle reaction 40h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.7% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -53 DEG C, cooling time 5h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 23Pa, and built-in temperature is -54 DEG C, drying time 56h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 6
Step 1：Take and soak 19h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 14500r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 42000r, then by original
It is that 2.2% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.26g zinc nitrate hexahydrates are dissolved in 11g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 10.28%；23g 2-methylimidazoles are dissolved separately in 33g deionized waters again,
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 41.07%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 9min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 4min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 70 DEG C of oil bath environment
Middle reaction 47h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.9% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -56 DEG C, cooling time 5.5h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 24Pa, and built-in temperature is -55 DEG C, drying time 48h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 7
Step 1：Take and soak 20h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 14800r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 45000r, then by original
It is that 2.3% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.30g zinc nitrate hexahydrates are dissolved in 10g deionized waters under room temperature condition, obtain solution A, its
The mass concentration of middle zinc nitrate hexahydrate is 11.50%；33g 2-methylimidazoles are dissolved separately in 35g deionized waters again,
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 48.53%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 5min in step 3, solution B is poured into fibrous suspension II immediately
In, continue mechanical agitation 9min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 72 DEG C of oil bath environment
Middle reaction 45h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 1.6% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -56 DEG C, cooling time 6h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 25Pa, and built-in temperature is -56 DEG C, drying time 50h, so as to obtain efficient air
Body absorbent-type air filting material.
Embodiment 8
Step 1：Take and soak 20h equivalent to oven-dry weight 15g string pulpboards, recycle standard fluffer to disperse
Fleeces aggressiveness 15000r, after the abundant swollen of fiber is discongested, then fibrillation processing being carried out, defibrination revolution is 50000r, then by original
It is that 2.5% fibrous suspension I is standby that fibrillated fibers, which are diluted with water and are made into mass concentration,；
Step 2：1.34g zinc nitrate hexahydrates are dissolved in 9g deionized waters under room temperature condition, obtain solution A, wherein
The mass concentration of zinc nitrate hexahydrate is 13%；36.67g 2-methylimidazoles are dissolved separately in 30g deionized waters again, obtained
Solution B is obtained, the wherein mass concentration of 2-methylimidazole is 55%；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it.Utilize six water
Close zinc nitrate solution and exchange of solvent is carried out to fibrous suspension I, make Zn2+Adsorbed by electrostatic adsorption in electronegative fiber
Surface, while obtain and carry Zn2+Fibrous suspension II；
Step 4：After suspension II mechanical agitation 10min in step 3, solution B is poured into fibrous suspension immediately
In II, continue mechanical agitation 10min, so as to obtain milky suspension II I；
Step 5：Suspension II I in step 4 is poured into ptfe autoclave, in 75 DEG C of oil bath environment
Middle reaction 48h.After reaction terminates, the fiber of load ZIF-8 crystal is isolated by vacuum filtration method, and utilize deionized water pair
It is cleaned for several times, to remove water-solubility impurity；
Step 6：Water is added to be made into the fibre that mass concentration is 2.0% fiber of the load ZIF-8 crystal prepared in step 5
Dilution is tieed up, then fiber dilution liquid is poured into glass culture dish, is positioned in freeze drier, freeze forming condition is：It is cold
It is -56 DEG C, cooling time 6h to freeze temperature, so as to complete the preliminary freeze forming of sample；
Step 7：Treat that sample freezes reality completely, carried out freeze-drying process, concrete operations are that sample is moved into freezing to do
Dry machine removes ice crystal, and its vacuum is arranged to 25Pa, and built-in temperature is -56 DEG C, drying time 50h, so as to obtain efficient air
Body absorbent-type air filting material.
Fig. 1 is the process chart of the present invention.Fig. 2 is then the microscopic appearance that blank Example and embodiment 3 prepare filter material
Contrast.Primordial plant fiber is can be seen that from Fig. 2-a, and network structure is presented by defibrination process, but due to pristine fibre
Specific surface area is generally 2~4m2/ g, therefore only with cellulose base air filtration prepared by simple freeze-drying process technology
The specific surface area of material can only achieve 6~12m2The effective collision area of/g, particulate and filter material is smaller, so as to limit it to micro-
The absorption property of grain.Additionally while string is a kind of porous material in itself, but its absorption to toxic gas it is micro- its
It is micro-.And by Fig. 2-b, it is apparent that ZIF-8 crystal has successfully been wrapped in the internal structure of filter material, additionally, due to ZIF-
The special pore passage structure of 8 crystal itself makes it have very big specific surface area and gas absorption property, so that through ZIF-8 crystal
Seizure and interdiction capability enhancing of the cellulose base air filting material of modification to particulate, while also have to toxic gas certain
Suction-operated.
Influence of the ZIF-8 crystal to the strainability of filter material is as shown in table 1：
Influence of the table 1ZIF-8 crystal to the strainability of filter material
Note：Test particulate matter is DEHS aerosols, particle diameter 300nm.
From table 1, it is apparent that compared to blank Example, the fibre modified through ZIF-8 crystal that is prepared in embodiment 3
The strainability for tieing up plain base air filter material is obviously improved, to the interception capacities of 300nm particulate matters up to 99.99%.This master
If due to the ZIF-8 nanocrystal layers of fiber surface parcel, fiber surface is set to become more coarse, when particulate matter and fiber
When surface collides, contribute to crown_interception of the enhancing to particulate matter.The specific surface area of the filter material of ZIF-8 crystal modification simultaneously increases
Greatly, suction-operated of the filtering material to fine particle is improved, so as to improve its air filter efficiency.
Influence of the ZIF-8 crystal to the formaldehyde adsorption property of filter material is as shown in table 2：
Influence of the table 2ZIF-8 crystal to the formaldehyde adsorption property of filter material
As can be seen from Table 2, compared to blank Example, prepared in embodiment 3 after the modification of ZIF-8 nanocrystals
The adsorbance of cellulose base air filting material PARA FORMALDEHYDE PRILLS(91,95) significantly improves, and this is due to have open metallic site in structure
The introducing of ZIF-8 nanocrystals can improve the gas sorption ability of cellulose base air filting material.Passed through under normal temperature and pressure
The sub-optimal fusion algorithm of ZIF-8 modification air filting material PARA FORMALDEHYDE PRILLS(91,95)s can reach 33mg/g, be pristine fibre element base filtering material
More than 20 times.
Claims (10)
1. a kind of preparation method of efficient gas absorbent-type air filting material, it is characterised in that comprise the following steps：
Step 1：String is discongested, fibrillation processing, obtain finely dispersed fibrous suspension I；
Step 2：Zinc nitrate hexahydrate is dissolved in deionized water under room temperature condition, obtains solution A, then by 2-methylimidazole
It is dissolved separately in deionized water, obtains solution B；
Step 3：Solution A is poured into fibrous suspension I, is stirred continuously in addition, is sufficiently mixed it, utilizes six hydration nitre
Sour zinc solution carries out exchange of solvent to fibrous suspension I, makes Zn2+Adsorbed by electrostatic adsorption in electronegative fiber table
Face, acquisition carry Zn2+Fibrous suspension II；
Step 4：After fibrous suspension II is stirred, solution B is poured into fibrous suspension II immediately, continues to stir,
So as to obtain fibrous suspension III；
Step 5：Suspension II I is poured into ptfe autoclave, reacted in oil bath environment, after reaction terminates, is led to
The fiber that vacuum filtration method isolates load ZIF-8 crystal is crossed, and the fiber for loading ZIF-8 crystal is cleaned using deionized water
Several times；
Step 6：The fiber for the load ZIF-8 crystal that step 5 obtains is configured to fiber dilution liquid, fiber dilution liquid is put into
Freeze forming is carried out in shaping vessel, obtains frozen samples；
Step 7：Frozen samples are subjected to freeze-drying process, remove ice crystal so as to obtain efficient gas absorbent-type air filtration
Material.
A kind of 2. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
Step 1 is specifically that string pulpboard is soaked into 12~20h, discongests 12000~15000r, then carries out defibrination process,
Defibrination revolution is 20000~50000r.
A kind of 3. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
Fibrous suspension I mass concentration is 1.5~2.5% in step 1.
A kind of 4. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
The mass concentration of zinc nitrate hexahydrate is 8~13% in solution A described in step 2.
A kind of 5. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
The mass concentration of 2-methylimidazole is 30~55% in solution B described in step 2.
A kind of 6. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
Fibrous suspension I, solution A and solution B mass ratio are (600~1000)：(10.04~13.34)：(47.14~
76.67)。
A kind of 7. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
Oil bath temperature is 60~75 DEG C in step 5, and the reaction time is 24~48h.
A kind of 8. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
The concentration of fiber dilution liquid in step 6 is 1.5~2%.
A kind of 9. preparation method of efficient gas absorbent-type air filting material according to claim 1, it is characterised in that
Freeze forming condition is in step 6：Cryogenic temperature is -45~-56 DEG C, and cooling time is 3~6h.
10. a kind of preparation method of efficient gas absorbent-type air filting material according to claim 1, its feature exist
In freeze-drying process condition is in step 7：Drying temperature is -45~-56 DEG C, and drying time is 48~56h, drying process
Vacuum be 15~25Pa.
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| WO2022095097A1 (en) * | 2020-11-09 | 2022-05-12 | 苏州纳昇源新材料科技有限公司 | Method for preparing fully biodegradable high-efficiency air composite filter material |
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