The nanofiber of resistance to blowback Compound filtering material and preparation method thereofTechnical field
The present invention relates to filtering material fields, and in particular to a kind of nanofiber of resistance to blowback Compound filtering material and its preparation sideMethod.
Background technique
Current air pollution problems inherent is concerned, and world's advocating environment protection high-efficiency environment friendly utilizes the energy.Gas turbine inlet airSystem and industrial dedusting system to filtering substrate technical indicator from filter efficiency, resistance pressure drop, dust containing capacity, service life several notIt is disconnected to propose higher standard requirements.High-pressure electrostatic, which spins prepared nano-scale fiber net air filtering material, efficient, low-resistance feature.Nanofiber composite air filter material and deep layer air filtration filter material compare the filtration mechanism due to nanofiber composite air filter materialIt is to capture particle overwhelming majority particle packing in surface of filter medium based on the mechanical interception of surface, setting dynamic pulse can be passed throughBlowback is purified and is recycled, and has higher dust containing capacity longer if it can reach in the technical indicator actual use of resistance to blowbackService life.
Current high-pressure electrostatic spinning nano fibre composite filtering material is that gas turbine inlet air system industrial dust-collecting air system is bestOne of filtrate.Technological break-through realization industrial volume production has Donanldson, Finetex Mats in the worldTM,AntimicrobeWebTM, NanoFilterTM, Fibra-WebTMBrand quotient.It is being removed outside Donanldson by investigation, Quan ShouLifeblood, which is rushed in blowback air-flow cleaning process, all there is the defect that different degrees of nanometer fiber net falls off from substrate, causes circulation anti-It blows rear filter efficiency and dust containing capacity constantly declines, filter runing time serious curtailment increases use cost.
Domestic filter material technology falls behind relatively, from military (052 serial warship, 055 serial warship) to civilian Power Plant Gas Turbine intoThe high-end filter core filter material of the gas system market (F9 class criteria EN779-2012) is by external (Donanldson) monopolization, according to the investigation countryEnterprises and institutions and technology universities and colleges rest on laboratory stage to high-pressure electrostatic spinning nano fibre technology majority, from equipment to technique volume productionThere are also many technical matters to need to break through for nanofiber Compound filtering material.Such as: CN101940856A and CN102908829A patentThe technical indicator cleaned due to not accounting for life-cycle pulse backblowing in preparation, easily causes the broken ring of nanofiber wire side,Product, which can not provide in the case where dynamic pulse blowback for gas turbine, stablizes good air.In CN104028047B patentMake the technical solution for generating adhesion between fiber there are safety problem using solvent vapo(u)r, realizes that wear-resisting, antistripping method hasThere is very big security risk.It is known that operating voltage is often up to tens of thousands of volts during high-voltage electrostatic spinning mass production, control is highStrong middle solvent steam concentration of having a meeting, an audience, etc. well under one's control is the prerequisite of safe volume production.All there is industrial production simultaneously in above-mentioned existing technical patentThe characteristics of difficulty is big, and production process is many and diverse, high production cost.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of the nanofiber of resistance to blowback Compound filtering material, the systemsPreparation Method disposal molding, simple process, production cost is low, the obtained Compound filtering material excellent performance of resistance to blowback.
It is an object of that present invention to provide a kind of preparation methods of the nanofiber of resistance to blowback Compound filtering material, comprising:
A fiber-like substrate is provided, conductive powder body is added during the preparation process to become static dissipative material in the substrate；And
By the method for electrostatic spinning polymer solution in at least one side of the fiber base material depositing of nanofibrous layer,Obtain the Compound filtering material.
Further, the minimum filter efficiency of the Compound filtering material is 60%.
Further, the substrate be manufactured paper with pulp by wet process papermaking technology the filter paper substrate prepared or by melt-blown legal systemStandby non-woven fabrics base material.Further, the weight of the filter paper substrate is 20~140gsm, and the weight of the non-woven fabrics base material is20~250gsm.
Further, the raw material of the filter paper substrate includes following component as mass fraction: 10~19.5% increasingStrong fiber, 5~7% conductive powder body and the wood pulp cellulose of surplus.
Further, the reinforcing fiber is selected from PET fiber and/or PP fiber, and diameter is preferably 50~70 μm, lengthPreferably 5~10cm, reinforcing fiber can increase the stiffness, burst and weatherability of fiber-like substrate.
Further, the raw material of the non-woven fabrics base material includes following component as mass fraction: 5~7% conductionThe polymer of powder and surplus, the polymer is in polyester fiber (PET), polypropylene, Kynoar, PA6, PA66At least one.
Further, the conductive powder body is selected from metal system conducting powder, metal oxide system conducting powder and carbon series conductiveAt least one of powder, the partial size of conductive powder body are 50~6000nm, preferably 50~300nm.Wherein, the metal conductive powderIncluding silver powder, aluminium powder and copper powder；The metal conductive oxide powder includes antimony-doped stannic oxide, Al-Doped ZnO and indium-doped oxidationTin；The carbon series conductive powder includes carbon fiber powder, conductive black, carbon nanotube and graphene.Preferably the conductive powder body isCarbon fibe powder, with good electric conductivity, ductility and dispersibility, and it is at low cost.
Further, the polymer in the polymer solution is selected from least one of materials described below: Kynoar,Polyurethane, polyacrylonitrile, polymethyl methacrylate, polylactic acid, polyamide, polyimides, Nomex, polybenzimidazoles,Polyethylene terephthalate, polypropylene, polyaniline, polyethylene oxide, poly- naphthalene diacid second diester, poly terephthalic acid fourth twoEster, SBR styrene butadiene rubbers, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinyl butylene and their copolymerOr derivative.
Further, Kynoar solution and polyurethane solutions that the polymer solution is 9:1~5:5 by mass ratioIt mixes；Made of the Kynoar solution is configured as the Kynoar that mass ratio is 1:9~20 and mixed solvent,The polyurethane solutions are as made of polyurethane and the mixed solvent configuration of mass ratio 1:9~15；The mixed solvent includes matterFor amount than the solvent A and solvent B that are 9:1~5:5, the solvent A is n,N-Dimethylformamide or n,N-dimethylacetamide, instituteStating solvent B is acetone or butanone.The advantages of combining two kinds of materials by Electrospun nano-fibers prepared by the polymer solution,The characteristics such as intensity height, good toughness, wear-resisting, cold-resistant, oil resistant, water-fast, ageing-resistant, weatherability are embodied, while there is high waterproofnessAntibacterial, mould proof, anti-ultraviolet characteristic.
It further, include the conductive auxiliary agent of 0.01%~0.5wt% in the polymer solution, to increase polymer spunThe electric conductivity of silk liquid.Preferably, the conductive auxiliary agent is tetrabutylammonium perchlorate.
Another aspect of the present invention additionally provides the nanofiber of resistance to blowback Compound filtering material prepared by the above method.
The principle of the present invention are as follows: in the present invention, by joined conductive powder body in substrate fiber, make the table of substrate fiberSurface resistance is in 104~1011Between Ω, become static dissipative material, the electrostatic charge of fiber surface is enabled to conduct in timeDissipation is gone out.When receiving Electrospun nano-fibers with the substrate, fall in charge on the nanofiber on substrate fiber due toThere is no accumulation conditions and dissipate, disappear quickly, and fall in the nanofiber in substrate fiber hole, the charge on surface is then continuousEnrichment, therefore the interpore nanofiber of substrate fiber finally generates potential difference with the nanofiber on substrate fiber by electret.Under the action of electrostatic force, the drop point of high-voltage electrostatic spinning nanofiber is more intended on substrate fiber, finally on substrateForm the greens (such as attached drawing 3, shown in 4) of random enrichment nanofiber.
The beneficial effects of the present invention are:
1. making the substrate of preparation become electrostatic by the way that conducting function powder is added in the preparation process of substrate in the present inventionDissipative material is tended to by the distribution of the effectively control electrostatic spinning nano fiber of the adjustment to substrate fiber electrostatic resistivity size,The contact area of nanofiber and substrate fiber is increased in the case where not obviously increasing resistance pressure drop, is received to enhanceThe adhesiveness of rice fiber and substrate, improves resistance to blowback performance.
2. nanofiber Compound filtering material disposal molding produced by the invention, simple process, production cost is low, properties of productIt is outstanding.On F6-F8 rank (EN779-2012 standard) filter paper being synthetically prepared by wood pulp cellulose and chemical fibre, pass through electrostatic sprayingNanofiber makes filter efficiency stably reach F9 (EN779-2012 standard) and the above rank.Resistance to blowback performance is perfect, warpThe resistance to pulse backblowing of test filter effect dust containing capacity and comprehensive performance reach the standard of international high-end air filtering material.
Detailed description of the invention
Fig. 1 is the schematic diagram of high-voltage electrostatic spinning apparatus single group used in embodiment and comparative example；
Fig. 2 is the Electronic Speculum sectional view of Compound filtering material prepared by embodiment 3, wherein 201 be nanoweb layer, 202 be baseMaterial layer；
Fig. 3 is nanofiber greens electron microscope in the Compound filtering material of the preparation of embodiment 3；
Fig. 4 is that nanofiber is distributed electron microscope in the Compound filtering material of the preparation of embodiment 3, wherein 401 be on substrate fiber pointsThe nanofiber enrichment region (nanofiber greens) of cloth, 402 be distribution nanofiber rarefaction in substrate gap；
Fig. 5 is the Phenom fiber metric figure of the nanofiber in Compound filtering material prepared by comparative example 3；
Fig. 6 is the Phenom fiber metric figure of the nanofiber in Compound filtering material prepared by embodiment 3；
Fig. 7 is the table after the composite nano fiber filter material blowback (@6kg@1000 times) of embodiment 3 (a) and comparative example 1 (b)Face shape appearance figure；
Fig. 8 is national grid test report.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be withIt more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
1, raw material
Polyurethane, Lu Borun lubrizol Estane TPU X595A-11 or Bayer TUP 9395AU；
Kynoar, French A Kema ARKEMA Kynar PVDF 761A；
Ao Silong SY5043AD CW substrate: filter efficiency F7, quality 118gsm, thickness 0.29, Air permenbility 193L 200Pal/m2/ s, 42.1 μm of average pore size, 50 ± 5%@of filter efficiency, 0.3 μm of DEHS@32L；
RC-T380 carbon fiber powder originates from the auspicious innovative material Science and Technology Ltd. in Jiangsu Province Lianyun Harbour, density 1.77g/cm3,Elongation 1.52%, carbon content 95.8%, ash 0.27%, water content 0.5%, partial size 4um, modulus 235Gpa, intensity4950Mpa, conductivity 1.2 × 10-3。
2, production equipment
The embodiment of the present invention prepares 8 groups of spinneret systems (spinneret syringe needle is arranged upward) using industrialization assembly line and carries out high pressureElectrospinning is received wherein industrialization high-pressure electrostatic spins assembly line as shown in Figure 1, it at least needs to configure following equipment: uncoil-stand 1Winding apparatus 2, spinneret room frame 3, receiving screen 4, high-voltage DC power supply 5, spinning head 6, spinneret group 7, spinneret pack support 8, conveyer belt9, transfer roller 10.The structure of spinning head and spinneret unit is detailed in CN201811180346.9 patent, with the industrialization high-pressure electrostaticIt spins the matched industrialization feed proportioning system of assembly line and liquid-supplying system is detailed in 105019042 B patent of CN, details are not described herein.SpraySilk unit is modular assembly, can be prepared according to output demand with 4 multiple assembling such as: 4 groups, 8 groups, 16 groups or more.
3, detection device
The instrument that the present invention uses has: TEXTEST FX3300 air permeability tester, Phenom Pro Electronic Speculum, PhenomFiber metric system, wins abundant 8100 pulse backblowing testboard, FRASER 730SRM at TSI 8130A filter efficiency testerSheet resistance tester.
Examples 1 to 4: the nanofiber of resistance to blowback Compound filtering material is prepared
(1) filter paper substrate is prepared
According to the ratio of table 1, wood pulp cellulose, reinforcing fiber and conductive powder body are configured to mixed slurry and pass through wet process copy paperTechnology manufactures paper with pulp and prepares filter paper substrate.The weight of obtained filter paper substrate is 110gsm, and Air permenbility is 250L@200Pal/m2/ s,Average pore size is 56 μm, and filter efficiency is 30 ± 5%@, 0.3 μm of DEHS@32L.
The formula of 1 filter paper substrate of table
| Wood pulp cellulose (wt%) | Reinforcing fiber (wt%) | Conductive powder body (wt%) |
| Embodiment 1 | 80 | 17 | 3 |
| Embodiment 2 | 80 | 15 | 5 |
| Embodiment 3 | 80 | 13 | 7 |
| Embodiment 4 | 80 | 11 | 9 |
(2) nanofiber is prepared on filter paper substrate
Mixed solution parameter: solute material: Kynoar solution and polyurethane solutions ratio are 7:3, solution solid content:9%wt, conductive auxiliary agent: 0.1% tetrabutylammonium perchlorate, solvent: 90.9%DMF/MEK8:2, viscosity: 220 ± 5cP, conductanceRate: 300 ± 5 μ S/cm.
Production environment: constant temperature and humidity workshop, temperature (25 ± 2) DEG C, relative humidity (25 ± 5) %, enthalpy (37 ± 5) kJ,Assembly line fresh-air volume 18000m3/ h recycles air quantity (air draft) 18100m3/ h, pneumatics (2.5 ± 0.5) Pa in equipment, solvent gasBulk concentration < (10 ± 0.5) ppm.
Manufacturing parameter: amount of solution 700g/h, spinning height 120mm, spinneret group velocity of displacement 45mm/s, shift length50mm, spinning voltage 60kv, 8.8 meters/min of speed.
Preparation process:
The filter paper substrate of Examples 1 to 4 preparation is entered to the spinning stream for being provided with 8 groups of spinning packs by uncoil-stand 1In waterline, ingredient and feed flow are carried out by industrialization feed proportioning system and liquid-supplying system, under the action of high voltage electric field, are located at thousands ofThe solution of a spray head top end is enriched a large amount of charges and forms electrostatic repulsion forces, overcomes solution surface tension and itself glutinous elastic forceIt forms electrified jet fast uplink and is drafted, the very fast evaporating solution of solvent is formed by curing nano-scale fiber uniform deposition in substrateOn, it loops finally by wrap-up 2, obtains Compound filtering material.
The parameter of the Compound filtering material of embodiment 1-4 preparation is as shown in table 2:
The performance parameter of the Compound filtering material of 2 embodiment 1-4 of table preparation
It is measured by Phenom fiber metric system, the diameter of nanofiber is concentrated in the Compound filtering material of embodiment 31864nm is concentrated in the hole of 249~331nm, nanometer fiber net2(see Fig. 6), 0 μm of average pore size.
Comparative example 1
Mixed solution parameter: solute material: Kynoar solution and polyurethane solutions ratio are 7:3, solution solid content:9%wt conductive auxiliary agent: 0.1% tetrabutylammonium perchlorate, solvent: 90.9%DMF/MEK8:2, viscosity: 220 ± 5cP, conductanceRate: 300 ± 5 μ S/cm；
Production environment: constant temperature and humidity workshop, temperature (25 ± 2) DEG C, relative humidity (25 ± 5) %, enthalpy (37 ± 5) kJ,Assembly line fresh-air volume 18000m3/ h recycles air quantity (air draft) 18100m3/ h, pneumatics (2.5 ± 0.5) Pa in equipment, solvent gasBulk concentration < (10 ± 0.5) ppm.
Manufacturing parameter: amount of solution 700g/h, spinning height 120mm, spinneret group velocity of displacement 45mm/s, shift length50mm, spinning voltage 60kv, 10 meters/min of speed.
Using this dragon SY5043AD CW substrate difficult to understand as filter paper substrate, high-voltage electrostatic spinning nanofiber is prepared on substrate,The process of preparation is the same as embodiment 1.
Fibre diameter, which is measured, by Phenom fiber metric system concentrates on 270~396nm, nanometer fiber netHole concentrates on 2139nm2(see Fig. 5).It is by the Air permenbility that TEXTEST FX3300 air permeability tester measures Compound filtering material157L@200Pal/m2/s.It is 80 ± 5%@by the filter efficiency that TSI 8130A filter efficiency tester measures Compound filtering material0.3μm DEHS@32L。
The resistance to blowback test of pulse
Using winning the resistance to of Compound filtering material prepared by abundant 8100 pulse backblowing testboard difference testing example 3 and comparative example 1Blowback performance, blowback air pressure are 3~6kg, and blowback area is 50.24cm2, blowback number is 1000 times, acquired results such as 3 institute of tableShow.
The resistance to blowback test result of 3 comparative example 1 of table and 3 sample of embodiment
According to the resistance to blowback data of the pulse of table 3 it can be found that on this difficult to understand dragon SY5043AD CW substrate electro spinning nano fiberObtained Compound filtering material, in the case where pulse backblowing air pressure is 4~5kg, being decreased obviously occurs in filter efficiency；Work as blowback airFilter efficiency has dropped 30% or so when pressure increases to 6kg.By the electron microscope of Fig. 7 it can be found that the Compound filtering material of comparative example 1There is serious disrepair phenomenon.
And the resistance to blowback of Compound filtering material prepared by embodiment 3 is had excellent performance, the filter efficiency when blowback air pressure is 3~5kgDo not decline, when blowback air pressure increases to 6kg, filter efficiency is still without there is apparent decline.Pass through Fig. 7'sElectron microscope is not it can be found that breakage occurs in the Compound filtering material surface.
Referring to the national grid test report of Fig. 8, the Compound filtering material of embodiment 3 is reaching F9 (EN779-2012 standard)In the case of filter efficiency, but without there is apparent resistance pressure drop.This is because the Compound filtering material of embodiment 1 increases NanowireThe contact area of peacekeeping substrate enhances the adhesiveness of nanometer fiber net and substrate, to realize excellent resistance to blowback performance.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the inventionIt encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present inventionProtection scope within.Protection scope of the present invention is subject to claims.