CN106178696B - Nano-fiber material and preparation method for mercury polymorphic in atmosphere acquisition - Google Patents

Nano-fiber material and preparation method for mercury polymorphic in atmosphere acquisition Download PDF

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CN106178696B
CN106178696B CN201610523782.6A CN201610523782A CN106178696B CN 106178696 B CN106178696 B CN 106178696B CN 201610523782 A CN201610523782 A CN 201610523782A CN 106178696 B CN106178696 B CN 106178696B
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mercury
nanofiber
preparation
nano
polymorphic
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CN106178696A (en
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康学军
柳雄威
黄晶晶
卫兰兰
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Southeast University
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Southeast University
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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
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • 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
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/546—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using nano- or microfibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D—TEXTILES; PAPER
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
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    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/706—Organometallic compounds

Abstract

The present invention is a kind of nano-fiber material and preparation method for mercury polymorphic in atmosphere acquisition, which is the multifunctional macromolecule nanofiber of the area load sulfydryl of one-step shaping.The preparation method comprises the following steps: in a solvent by high molecular polymer dissolution, stirring is made into spinning solution；It is made again of reagent of the solvent dissolution containing sulfydryl and is added into the spinning solution after solution；It chooses in one of 4- methoxyl group -2,6- tert-butyl phenol BHA, 4- methyl -2,6 di t butyl phenol BHT, tert-butyl hydroquinone TBHQ and propylgallate PG, sulphite addition spinning solution and plays anti-oxidant stabilization；Acetate, citrate, carbonate, hydroxide or ammonium salt is added and adjusts medium pH value；Using electrostatic spinning technique, nanofiber, filter membrane processed after cutting are received by substrate material of breathable film material；Nanofiber is received using fine and close airtight thin-film material as substrate material again, with nanofiber together with substrate preparative layer stacked column.

Description

Nano-fiber material and preparation method for mercury polymorphic in atmosphere acquisition
Technical field
It is that the polymorphic mercury of trace carries out sampling trapping in a kind of pair of atmosphere the invention belongs to atmosphere environment supervision technical field Nano-fiber material preparation and application.
Background technique
Mercury is a kind of high toxicity heavy metal with bioconcentration, it is present in sky gas and water and soil.There are many mercury Existence form, including element mercury, inorganic mercury and organic mercury.Mercury and mercuric compounds are important environmental contaminants, and coal combustion is big One main source of bicycle pump pollution, studying it oneself becomes the advanced problems of current Environmental Studies.Mercury be also it is unique mainly with Gaseous form is present in the heavy metal contaminants of atmosphere.Atmospheric environment is the important place of mercury Transport And Transformation, in atmospheric environment Mercury is broadly divided into according to physical chemistry form: gaseous elemental shows (Hg0, Gaseous Elemental Mercury, GEM), activity Gaseous mercury (Hg2+, Reactive Gaseous Mercury, RGM) and particle mercury (pHg, Particle Mercury, absorption In Atmospheric particulates) three kinds.
Currently, the gaseous elemental mercury in atmosphere is mainly adsorbed using gold-plated quartz sand, and particle mercury then uses stone English fibrous filter membrane is trapped, and reactive gaseous mercury is generally absorbed with diffusion denuder method.In practical applications, it is difficult to by the unified knot of three It closes, and adsorption efficiency is difficult to improve.
Summary of the invention
Technical problem: the object of the present invention is to provide it is a kind of for mercury polymorphic in atmosphere acquisition nano-fiber material and Preparation method, its high molecular material of the method for electrostatic spinning and modification reagent can be matched arbitrarily, therefore can readily prepare New material containing various functional characteristics (such as Adsorption of Mercury effect, sulfydryl stabilization and protective effect).Manufactured material is due to it The efficiency of unique surface characteristic, trapping mercury is significantly improved than current material.
Technical solution: the invention proposes be polymorphic mercury in filtrate acquisition air with novel functional nano fibrous membrane. Using the functional new material of the method preparation trapping mercury of sulfydryl modification electro spinning nano fiber.According to " soft-hard acid-base theory ", mercapto Base can form stable complex with the soft heavy metal (Hg, Ag, Au) with strong polarizability, weaker with the effect of Cd and Zn, And do not have an effect with light metals such as Ca, Na, Mg, sulfydryl material is that a kind of generally acknowledged adsorption capacity is big, selectivity is high, absorption effect The good mercury adsorbent material of fruit.Sulfhydryl Cotton is exactly a kind of fiber profile that mercury can be trapped made of sulfydryl functional group modification cotton Material, but preparation method needs plurality of reagents (corrosive reagents such as including strong acid) long period (a couple of days) under certain condition Reaction preparation.The present invention takes one step of method of electrostatic spinning that can prepare the Nanowire d type mercury that sulfydryl functional group is modified Material for trapping, preparation process do not have to strong corrosive reagent.
A kind of nano-fiber material for mercury polymorphic in atmosphere acquisition of the invention is the area load of one-step shaping The multifunctional macromolecule nanofiber of sulfydryl.
The nano-fiber material for mercury acquisition polymorphic in atmosphere of the invention the preparation method comprises the following steps: by high molecular polymerization Object dissolves in a solvent, and stirring is made into spinning solution；It is made again of reagent of the solvent dissolution containing sulfydryl described in being added into after solution Spinning solution；Choose 4- methoxyl group -2,6- tert-butyl phenol (BHA), 4- methyl -2,6 di t butyl phenol (BHT), tert-butyl hydrogen One of quinone (TBHQ) and propylgallate (PG), sulphite are added in spinning solution and play anti-oxidant stabilization；Add Enter acetate, citrate, carbonate, hydroxide or ammonium salt and adjusts medium pH value；Using electrostatic spinning technique, with ventilative Property thin-film material be substrate material receive nanofiber, filter membrane processed after cutting；Again using fine and close airtight thin-film material as substrate material Material receives nanofiber, with nanofiber together with substrate preparative layer stacked column.
The high molecular polymer be polyphenylene sulfide, acetic acid element, polystyrene, polycaprolactam, acrylic resin or One or several kinds of mixing of polyacrylonitrile.
The solvent is n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, third or formic acid.
The reagent containing sulfydryl is thioacetic acid and its esters, mercapto-polyglycol, mercaptoethylmaine salt, mercaptoethanol Or one or several kinds of mixing of cysteine and its derivative.
Working principle
Dredging based compound has coordination ability to mercury in micro acid medium, can inhale respectively organic mercury with inorganic mercury Attached and desorption, can be used for the collection of mercury in atmosphere.Its effect equation is as follows:
Since the specific surface of nanofiber is larger, trapping mercury capacity is correspondingly also larger；Due also to having in nanofiber Many holes, thiol molecule are carried on the surface of nanofiber, due to capillarity, are easy to act on mercury, generate the thin base of mercury Complex.It, which collects effect, can avoid the screen effect and passivation phenomenon of this kind of collectors of amalgam processes such as gold, silver, therefore catch It is good to collect mercury effect.In addition, the composition fiber of electrostatic spinning non-woven fibre film has smaller compared with traditional fiber filter material Diameter (usually less than 500mn), therefore under same pressure drop, diffusion of the gas in the lesser fiber peripheral flowing of diameter, It intercepts and inertial collision frequency increases, thinner nanofiber is formed by non-woven fibre film to the capture ability of tiny particles content It is stronger, therefore can be with efficient capture air particle, especially fine grained.And metallic element is adsorbed more by fine grained, therefore Nano-fiber material also significantly improves mercury metal arresting efficiency in air particle.
The utility model has the advantages that
1) various reagents wiring solution-forming is mixed, one-step method can prepare the material of efficiently trapping object, material is made It can take into account and stablize, keep functional group activity, the functions such as media environment condition needed for maintaining suction-operated；
2) specific surface area of nanofiber made of is larger, have it is more with object interaction sites so that green wood Material greatly improves object arresting efficiency；
3) high porosity of nano-fiber material and skin effect make it have both gaseous material absorption and particulate matter interception, catch Collection effect, and then it is suitable for the trapping of the variforms mercury such as gaseous state, particulate matter mercury.
Detailed description of the invention
Several filter membrane material acquisition air-borne mercury efficiency of Fig. 1 compare.
Two kinds of film pictorial diagrams of Fig. 2 and acquisition air-borne mercury efficiency compare.
Specific embodiment
By high molecular polymer (such as polyphenylene sulfide, acetic acid element, polystyrene, polycaprolactam, acrylic resin, poly- third One or several kinds of mixing such as alkene nitrile) it is dissolved in a certain proportion of solvent (such as n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, third Ketone, formic acid etc.) in, stirring is made into spinning solution.Choose solvent appropriate (such as n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, Acetone, formic acid etc.) dissolution in right amount the reagent containing sulfydryl (such as thioacetic acid and its esters, mercapto-polyglycol, mercaptoethylmaine salt, One or several kinds of mixing such as mercaptoethanol, cysteine and its derivative) solution is made after be added into spinning solution.Choose 4- methoxy Base -2,6- tert-butyl phenol (BHA), 4- methyl -2,6 di t butyl phenol (BHT), tert-butyl hydroquinone (TBHQ) and galla turcica Anti-oxidant stabilization is played in one of propyl propionate (PG), sulphite or several appropriate addition spinning solutions.It is appropriate to be added Acetate, carbonate, hydroxide, ammonium salt, adjusts medium pH value at citrate.Using electrostatic spinning technique, with appropriate Fabric is to receive (gas permeability substrate receives filter membrane processed after nanofiber, and fine and close airtight substrate receives column processed after nanofiber), Thiol functionality nanofiber is spinned in substrate surface, a step, that is, plastic is fabricated to filter membrane, Huo Zhecan after cutting together with substrate Stacked pillar is made according to the method for Patent No. 201410143082.5.Nano fibrous membrane is mounted on to the sampling being dimensioned for On folder, or by the suitable pipe-line system of stacked pillar connection, it can be used for the efficient sampling of mercury in surrounding air.It is of the invention special Point is that the general adsorbent material of material amount ratio of nano fibrous membrane is few, small volume, easy to operate simple.And the technology Collect polymorphic object acquisition, concentrate in one, can reach micro, Trace Hg enrichment concentration.
The acquisition and measurement of mercury metal in atmosphere
(1) compared with quartz filter is commercialized
The films of a variety of materials (sulfydryl functional nano-fiber filter membrane is by taking the polystyrene film of cysteine modified as an example) Sampling folder is mounted on sampler, in sampled point operation repetitive, with the flow collection air of 5L/min.
The filter membrane sampled is put into polytetrafluoroethylene beaker after being cleared up with nitric acid-hydrogen peroxide, and the nitre of 1+9 is added Sour 5ml extraction, is transferred in volumetric flask, with ultrapure water constant volume, shakes up, use Atomic Fluorescence Spectrometry after placing 30min.With same Method handle blank control filter membrane, prepare placebo solution with background correction value, measurement result is shown in Fig. 1.
Nano fibrous membrane after sulfydryl modification shows higher mercury adsorbing and trapping performance than other materials film, and its with The growth of acquisition time, tunica fibrosa is gradually increased the enriching quantity of mercury, and other two kinds of films extend at any time, and mercury enriching quantity increases Length is unobvious.
(2) compared with Sulfhydryl Cotton
Sulfhydryl Cotton is because its higher absorption property and relatively simple operation are considered as good mercury adsorbent material, still Sulfhydryl Cotton is not easy to prepare and save, and preparation process is relatively complicated, but it is still used as in a kind of common air at present The adsorbent of mercury.The present invention is control with it, in comparison by material of the invention.Sulfhydryl Cotton is according to industry standard methods system It is standby, its is evenly laid out in filter membrane is made on substrate material identical with nanofiber filter membrane.Equipped with a variety of materials film (sulfydryl Functional nano-fiber filter membrane is by taking cysteine modified film as an example) sampling folder be mounted on sampler, in sampled point operation repetitive, With the flow collection air of 5L/min.
The Sulfhydryl Cotton filter membrane sampled is desorbed according to standard method with 2mol/L hydrochloric acid, is surveyed after constant volume with atomic fluorescence method It is fixed.And nanofiber filter membrane is then put into polytetrafluoroethylene beaker after being cleared up with nitric acid-hydrogen peroxide, and the nitric acid of 1+9 is added 5ml extraction, is transferred in volumetric flask, with ultrapure water constant volume, shakes up, and uses Atomic Fluorescence Spectrometry after placing 30min.With same Method handles blank control filter membrane, prepares placebo solution with background correction value, measurement result is shown in Fig. 2.It can be seen that unit Quality is compared, and nano fibrous membrane is significantly higher than Sulfhydryl Cotton several times to the capture rate of air-borne mercury.

Claims (4)

1. a kind of preparation method of the nano-fiber material for mercury polymorphic in atmosphere acquisition, it is characterised in that: the Nanowire Tie up the multifunctional macromolecule nanofiber for the area load sulfydryl that material is one-step shaping；High molecular polymer is dissolved in solvent In, stirring is made into spinning solution；It is made again of reagent of the solvent dissolution containing sulfydryl and is added into the spinning solution after solution；Choose 4- Methoxyl group -2,6 di t butyl phenol, 4- methyl -2,6 di t butyl phenol, tert-butyl hydroquinone TBHQ and propylgallate, One of sulphite is added in spinning solution and plays anti-oxidant stabilization；Acetate, citrate, carbonate, hydrogen is added Oxide or ammonium salt adjust medium pH value；Using electrostatic spinning technique, received by substrate material reception of breathable film material Rice fiber, filter membrane processed after cutting；Or nanofiber is received using fine and close airtight thin-film material as substrate material, connected with nanofiber With substrate preparative layer stacked column.
2. the preparation method for the nano-fiber material of mercury acquisition polymorphic in atmosphere as described in claim 1, feature Be: the high molecular polymer is polyphenylene sulfide, polystyrene, polycaprolactam, acrylic resin or polyacrylonitrile One or several kinds mixing.
3. the preparation method for the nano-fiber material of mercury acquisition polymorphic in atmosphere as described in claim 1, feature Be: the solvent is n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol or formic acid.
4. the preparation method for the nano-fiber material of mercury acquisition polymorphic in atmosphere as described in claim 1, feature Be: the reagent containing sulfydryl is thioacetic acid and its esters, mercapto-polyglycol, mercaptoethylmaine salt, mercaptoethanol, half One of cystine and their derivative or several mixing.
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