CN113926437B - Preparation method and application of degradable VOCs adsorption material - Google Patents
Preparation method and application of degradable VOCs adsorption material Download PDFInfo
- Publication number
- CN113926437B CN113926437B CN202111240996.XA CN202111240996A CN113926437B CN 113926437 B CN113926437 B CN 113926437B CN 202111240996 A CN202111240996 A CN 202111240996A CN 113926437 B CN113926437 B CN 113926437B
- Authority
- CN
- China
- Prior art keywords
- filter material
- degradable
- vocs
- temperature
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 title abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000012545 processing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 241001589086 Bellapiscis medius Species 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 44
- 238000005507 spraying Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 19
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 19
- 238000009998 heat setting Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000009960 carding Methods 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 7
- 235000020679 tap water Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000003490 calendering Methods 0.000 claims description 6
- 239000012792 core layer Substances 0.000 claims description 6
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000009999 singeing Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 230000000274 adsorptive effect Effects 0.000 claims 6
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005129 volume perturbation calorimetry Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B01J35/58—
-
- 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
- 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
- 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
-
- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a preparation method of a degradable VOCs adsorption material, which comprises the following steps: preparation of the blend: fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use; (2) spinning the sheath-core structure; and (3) elasticizing: the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 250-300m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the temperature of the upper hot box is 120-140 ℃, and the temperature of the lower hot box is 110-130 ℃; and (4) processing the filter material. The filter material with excellent VOCs degradation and adsorption performance is successfully obtained by adopting the technical scheme disclosed by the invention.
Description
Technical Field
The invention relates to the field of preparation of degradable adsorption VOCs materials, in particular to a preparation method and application of the degradable adsorption VOCs material.
Background
The outdoor VOCs are mainly derived from combustion of fuels such as petroleum and coal, chemical industry, emission of vehicle tail gas and the like. Indoor VOCs mainly come from indoor decorative materials, such as wall paint, furniture paint and the like, and all can cause volatilization of VOCs gas, so that indoor air quality is reduced.
With the improvement of life quality and the enhancement of environmental awareness of people, the problem of environmental pollution caused by energy consumption is getting more and more attention from various communities, especially, various decoration materials such as home decoration, automobile interior decoration and the like are used, various organic compounds such as benzene, toluene, xylene and the like are released, and serious threat is caused to the health of people when people work for a long time or live in the environment.
Based on this, many technical improvements for degrading VOCs are reported, for example, the chinese patent application No.: CN202110846757.2 discloses an integrated device for degrading VOCs and sterilizing by microwave excitation ultraviolet light catalysis, and the following technical scheme is disclosed in the patent:
microwave excitation ultraviolet light catalytic degradation VOCs and integrated device that disinfects, microwave excitation ultraviolet light catalytic degradation VOCs and integrated device that disinfects include: the novel ultraviolet radiation type microwave oven comprises an oven body, a microwave emission device, an ultraviolet device and a catalyst device, wherein an air inlet and an air outlet are formed in two opposite ends of the oven body, the microwave emission device is connected to the top of the oven body, the ultraviolet device is arranged inside the oven body and can emit 185nm and 254nm ultraviolet light under the action of microwaves, the catalyst device is arranged inside the oven body, and the catalyst device is used for degrading VOCs under the action of the microwaves. The degradation and sterilization of VOCs are realized through the synergistic effect of microwave ultraviolet and a catalyst.
Obviously, the technical scheme disclosed in the prior art including the patent adopts a microwave ultraviolet catalytic degradation mode, and the disadvantage of the mode is that: low degradation rate, narrow application range and poor universality.
Disclosure of Invention
The invention aims to provide a preparation method of a degradable VOCs adsorption material.
The invention solves the technical problems through the following technical scheme:
a preparation method of a degradable VOCs adsorption material comprises the following steps:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 250-300m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the temperature of the upper hot box is 120-140 ℃, and the temperature of the lower hot box is 110-130 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the elasticizing treatment in the step (3) into a filter material.
Preferably, the graphene powder in the step (1) accounts for 2.5-6.25% of the total blend.
Preferably, the PLA-modified resin particles in step (1) are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.1kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
Preferably, the PLA-modified resin particles in step (1) are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.15kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
Preferably, the PLA-modified resin particles in step (1) are: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.3kg, antioxidant is: 28g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
Preferably, the PLA-modified resin particles in step (1) are: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.39kg, antioxidant: 28.5g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
Preferably, the method for processing the filter material in the step (4) is as follows:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 15-35% of the total weight of the filter material.
And spraying on the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min.
Performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
Preferably, the mass ratio of the sodium dodecyl benzene sulfonate, the grapheme carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:5:3:40:50.
Preferably, the mass ratio of the sodium dodecyl benzene sulfonate, the grapheme carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:7:1:40:50.
The invention also discloses application of the preparation method of the degradable adsorption VOCs material in preparation of filter materials.
Compared with the prior art, the invention has the following advantages:
the invention discloses a preparation method of degradable adsorption VOCs material, in the preparation method, based on melt spinning and elasticizing technology, PLA/EVA/GO/TIO2 blend fiber with high adsorption and degradability is prepared first; the VPCs (volatile organic compounds) have good mechanical properties, excellent adsorption effect of the VPCs such as dimethylbenzene and the like, obvious photocatalytic oxidation effect after adsorption, capability of decomposing the VOCs into water and carbon dioxide, realization of cyclic regeneration, no pollution, environment friendliness, and capability of being used for packaging materials of furniture and chemical building materials and interior decoration materials of indoor and transportation means.
Drawings
Fig. 1 is a schematic diagram of the structure of a filter material in a comparative example of the present invention.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
A preparation method of a degradable VOCs adsorption material comprises the following steps:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
wherein, PLA modified resin particles are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.15kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 280m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the upper hot box temperature is 135 ℃, and the lower hot box temperature is 120 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the texturing treatment in the step (3) into a filter material, wherein the processing method of the filter material comprises the following steps:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 15 percent of the total weight of the filter material.
And spraying on the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min.
Performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
Example 2
A preparation method of a degradable VOCs adsorption material comprises the following steps:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
wherein, PLA modified resin particles are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.15kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 250m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the upper hot box temperature is 140 ℃, and the lower hot box temperature is 130 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the texturing treatment in the step (3) into a filter material, wherein the processing method of the filter material comprises the following steps:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 35 percent of the total weight of the filter material. Wherein, the mass ratio of the sodium dodecyl benzene sulfonate, the graphene carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:7:1:40:50.
And spraying on the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min.
Performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
Example 3
A preparation method of a degradable VOCs adsorption material comprises the following steps:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
wherein, PLA modified resin particles are: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.3kg, antioxidant is: 28g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 280m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the upper hot box temperature is 130 ℃, and the lower hot box temperature is 120 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the texturing treatment in the step (3) into a filter material, wherein the processing method of the filter material comprises the following steps:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 20 percent of the total weight of the filter material. Wherein, the mass ratio of the sodium dodecyl benzene sulfonate, the graphene carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:7:1:40:50.
And spraying on the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min.
Performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
Example 4
A preparation method of a degradable VOCs adsorption material comprises the following steps:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
wherein, the PLA modified resin particles in the step (1) are as follows: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.39kg, antioxidant: 28.5g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 300m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the upper hot box temperature is 135 ℃, and the lower hot box temperature is 125 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the texturing treatment in the step (3) into a filter material, wherein the processing method of the filter material comprises the following steps:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 25 percent of the total weight of the filter material.
Wherein, the mass ratio of the sodium dodecyl benzene sulfonate, the graphene carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:7:1:40:50.
And spraying on the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min.
Performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
Comparative examples;
the high-performance chemical fibers prepared in examples 1 to 4 of the present invention were subjected to physical and chemical property tests, and the test results are shown in table 1:
table 1 performance test
As can be seen from table 1:
the fiber prepared by the invention has excellent physical and chemical properties.
The high-energy fiber is processed according to the step (4) of each embodiment to obtain a filter material, and as shown in fig. 1, the filter material comprises a micro-nano material hydrophobic layer 1 positioned on the top layer, a polyester and polypropylene mixed fiber layer 2 positioned below the micro-nano material hydrophobic layer 1, a base cloth layer 3 positioned below the polyester and polypropylene mixed fiber layer 2 and a mixed fiber layer 4 positioned at the bottom of the base cloth layer 3.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the degradable VOCs adsorbing material is characterized by comprising the following steps of:
(1) Preparation of the blend:
fully and uniformly mixing PLA modified resin particles, EVA, graphene powder and nano titanium dioxide, granulating by a double-screw extruder, drying, and putting into a dryer for drying for later use;
(2) Spinning of a sheath-core structure:
carrying out blending spinning on the dried material in the step (1), wherein in the spinning process, the temperature of a feeding hole of a core layer is controlled to be 200 ℃, and the temperature of a feeding hole of a skin layer is controlled to be 190 ℃; the temperature of the screw is 190 ℃; the pressure of the metering pump is 3.6MPa; winding speed: 3000m/min;
(3) And (3) texturing:
the blended yarn material processed in the step (2) is processed by texturing to obtain high-performance chemical fiber, in the texturing processing process, the production speed is controlled to be 250-300m/min, the I roller draft ratio is 1.4, the III roller underfeed rate is 96%, the black roller underfeed rate is 96%, the crossing angle is 10 ℃, the D/Y ratio of a false twister is 1.68, and the oiling rotating speed is 4.0; the temperature of the upper hot box is 120-140 ℃, and the temperature of the lower hot box is 110-130 ℃;
(4) And (3) processing a filter material:
processing the high-performance chemical fiber subjected to the elasticizing treatment in the step (3) into a filter material.
2. The method for preparing degradable adsorptive VOCs material according to claim 1, wherein the graphene powder in the step (1) accounts for 2.5-6.25% of the total blend.
3. The method for preparing degradable adsorptive VOCs material according to claim 2, wherein said PLA modified resin particles in step (1) are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.1kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
4. The method for preparing degradable adsorptive VOCs material according to claim 2, wherein said PLA modified resin particles in step (1) are: 3.35kg of ethylene-vinyl acetate copolymer: 0.5kg, graphene powder: 0.15kg, antioxidant is: 35g, stearic acid: 12.5g, nano titanium dioxide TiO 2 The method comprises the following steps: 8.1g.
5. The method for preparing degradable adsorptive VOCs material according to claim 2, wherein said PLA modified resin particles in step (1) are: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.3kg, antioxidant is: 28g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
6. The method for preparing degradable adsorptive VOCs material according to claim 2, wherein said PLA modified resin particles in step (1) are: 4.7kg of ethylene-vinyl acetate copolymer: 1.0kg, graphene powder: 0.39kg, antioxidant: 28.5g, stearic acid: 25g, nano titanium dioxide TiO 2 The method comprises the following steps: 12.1g.
7. The method for preparing the degradable adsorbing VOCs material according to claim 2, wherein the method for processing the filter material in the step (4) is as follows:
polyester fiber and polypropylene fiber are mixed according to the mass ratio of 1:1, feeding, opening, mixing, carding and lapping to obtain a first mixed layer fiber web;
opening, mixing, carding and lapping the high-performance chemical fibers to obtain a second mixed layer fiber web;
needling and solidifying the first mixed fiber layer, the base cloth and the second mixed fiber layer, and singeing and calendaring to obtain a semi-finished filter material;
preparing finishing liquid from sodium dodecyl benzene sulfonate, graphene carbon nanotubes, silicon dioxide, water and an adhesive, and performing ultrasonic pretreatment for 15min to prepare uniform spraying liquid; wherein the mass of the spraying liquid accounts for 15-35% of the total weight of the filter material;
spraying the surface of the first fiber layer by adopting a spraying device, and controlling the spraying speed to be 8m/min;
performing heat setting treatment on the spray-coated filter material;
wherein the temperature of the heat setting interval is as follows:
first 170 ℃, second 170 ℃, third 175 ℃, fourth 180 ℃, and fifth 180 ℃;
and obtaining the filter material after heat setting treatment.
8. The preparation method of the degradable adsorbing VOCs material according to claim 7, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the grapheme carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:5:3:40:50.
9. The preparation method of the degradable adsorbing VOCs material according to claim 7, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the grapheme carbon nano tube, the silicon dioxide, the tap water and the adhesive is as follows: 2:7:1:40:50.
10. Use of a method for preparing a degradable adsorptive VOCs material according to any one of claims 1 to 9 for preparing a filter material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111240996.XA CN113926437B (en) | 2021-10-25 | 2021-10-25 | Preparation method and application of degradable VOCs adsorption material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111240996.XA CN113926437B (en) | 2021-10-25 | 2021-10-25 | Preparation method and application of degradable VOCs adsorption material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113926437A CN113926437A (en) | 2022-01-14 |
CN113926437B true CN113926437B (en) | 2024-01-23 |
Family
ID=79284029
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111240996.XA Active CN113926437B (en) | 2021-10-25 | 2021-10-25 | Preparation method and application of degradable VOCs adsorption material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113926437B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105343925A (en) * | 2011-05-20 | 2016-02-24 | 宝洁公司 | A disposable article comprising fibers of polymer-wax compositions |
CN106179267A (en) * | 2016-08-01 | 2016-12-07 | 苏州锐特捷化工制品有限公司 | A kind of modified Nano of resistance to swelling fiber absorption construction substrate and preparation method thereof |
CN112452051A (en) * | 2020-11-04 | 2021-03-09 | 安徽元琛环保科技股份有限公司 | Preparation method of oxidation-resistant acid-alkali-resistant filter material and prepared filter material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108796817B (en) * | 2018-07-03 | 2019-05-10 | 南通志乐新材料有限公司 | A kind of melt-blown non-woven filter material |
-
2021
- 2021-10-25 CN CN202111240996.XA patent/CN113926437B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105343925A (en) * | 2011-05-20 | 2016-02-24 | 宝洁公司 | A disposable article comprising fibers of polymer-wax compositions |
CN106179267A (en) * | 2016-08-01 | 2016-12-07 | 苏州锐特捷化工制品有限公司 | A kind of modified Nano of resistance to swelling fiber absorption construction substrate and preparation method thereof |
CN112452051A (en) * | 2020-11-04 | 2021-03-09 | 安徽元琛环保科技股份有限公司 | Preparation method of oxidation-resistant acid-alkali-resistant filter material and prepared filter material |
Also Published As
Publication number | Publication date |
---|---|
CN113926437A (en) | 2022-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100465360C (en) | Optic catalyst anti-bacterial mildw-proof negative ion polypropylene monofilament and its preparing method and use | |
CN104452268B (en) | The preparation method of the fiber of load nano-titanium dioxide and the fiber obtained thereof | |
Sedghi et al. | A one step electrospinning process for the preparation of polyaniline modified TiO2/polyacrylonitile nanocomposite with enhanced photocatalytic activity | |
CN111892330A (en) | Superfine glass fiber cotton felt for photocatalytic air purification and preparation method thereof | |
CN102794039A (en) | Mix-type catalyst filter and manufacturing method thereof | |
CN101249271A (en) | Inorganic air purification material | |
CN102851943A (en) | Finishing method of automatic-cleaning textiles | |
Yang et al. | Fabrication of TiO 2/PI composite nanofibrous membrane with enhanced photocatalytic activity and mechanical property via simultaneous electrospinning | |
CN108265345A (en) | A kind of synthetic fibers with air-cleaning function and preparation method thereof | |
Zou et al. | Sulfated lignocellulose nanofibril based composite aerogel towards adsorption–photocatalytic removal of tetracycline | |
CN102319446A (en) | Material for air purification | |
Hua et al. | Preparation of visible light-responsive photocatalytic paper containing BiVO4@ diatomite/MCC/PVBCFs for degradation of organic pollutants | |
CN113926437B (en) | Preparation method and application of degradable VOCs adsorption material | |
Ge et al. | Electrospun polyurethane/loess powder hybrids and their absorption of volatile organic compounds | |
CN105214384A (en) | Air-conditioning special PM2.5 nonwoven fabric filter film and manufacturing process thereof | |
JP2007014851A (en) | Porous product | |
CN109157911A (en) | Nano-meter SiO_22Filtrate and its preparation and application is blended in modified ptfe needle thorn | |
CN206755425U (en) | A kind of novel air filtration | |
CN103007917A (en) | Preparation method of nano-zinc oxide/diatomite compound photocatalytic material | |
CN107537225A (en) | A kind of purification of air weaving filter cloth and preparation method thereof | |
CN110938890A (en) | Production method of polyester colored yarn | |
CN112452165A (en) | Ag/AgBr/AgVO3Composite nanofiber filtering membrane and preparation method and application thereof | |
CN109319877B (en) | Method for treating organic wastewater by using zirconia/titanium dioxide composite nanofiber material | |
Du et al. | Preparation and photocatalytic activity of bismuth tungstate coated polyester fabric | |
CN113862809B (en) | Preparation method of polymer fiber with water purification and ultraviolet resistance functions for fishing net |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |