CN114289007B - Preparation method of ternary purification material for garbage odor treatment - Google Patents
Preparation method of ternary purification material for garbage odor treatment Download PDFInfo
- Publication number
- CN114289007B CN114289007B CN202111645229.7A CN202111645229A CN114289007B CN 114289007 B CN114289007 B CN 114289007B CN 202111645229 A CN202111645229 A CN 202111645229A CN 114289007 B CN114289007 B CN 114289007B
- Authority
- CN
- China
- Prior art keywords
- mass
- parts
- photocatalytic
- nano
- titanium
- 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 43
- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 24
- 238000000746 purification Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229960000834 vinyl ether Drugs 0.000 claims description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000001621 bismuth Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 3
- RDLGTRBJUAWSAF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-2-one Chemical compound CC(=O)CC1C=CC=CC1(C)O RDLGTRBJUAWSAF-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-cyclohexyl Chemical group 0.000 claims description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 238000001523 electrospinning Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 34
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011206 ternary composite Substances 0.000 abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000032900 absorption of visible light Effects 0.000 abstract description 2
- 238000004887 air purification Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002120 nanofilm Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Abstract
The invention relates to preparation of an air purification material, and aims to provide a preparation method of a ternary purification material for garbage odor treatment. The invention loads nano carbon dots to Bi 2 O 3 Preparation of C@Bi on surface of nano short fiber 2 O 3 Composite material and then TiO is realized by controlling the hydrolysis of the titanium-containing precursor 2 Nanocrystalline at C@Bi 2 O 3 In-situ growth of composite material surface to utilize narrow band gap Bi 2 O 3 The nano short fiber absorbs visible light. The invention utilizes the nano carbon dots to improve TiO 2 With Bi 2 O 3 The photo-generated carrier migration capability between the two layers and further enhance the absorption of visible light, thereby constructing efficient TiO 2 @C@Bi 2 O 3 The ternary composite photocatalytic material has higher visible light catalytic activity. The two-step photocatalysis coating process solves the problem that the traditional method is to use high molecular film forming matters to catalyze nano particlesThe problem of degradation of the photocatalytic performance caused by the coating effect of the catalyst is solved, and the photocatalytic material is mainly positioned on the surface of the coating where the photocatalytic reaction occurs, and the photocatalytic material is not arranged in the coating, so that the waste of the photocatalytic material is avoided.
Description
Technical Field
The invention relates to preparation of semiconductor materials, in particular to a preparation method of a ternary purification material for garbage odor treatment.
Background
With the rapid promotion of urban construction in China, the production of household garbage is increased year by year. In order to reduce the environmental pollution caused by the disposal of household garbage, the disposal sites of the solid wastes of the large-scale household garbage are more and more far away from town centers, and thus garbage transfer stations are generated. The transfer station can be used for effectively collecting the dispersed household garbage uniformly, and the dispersed household garbage is compressed and then transferred to a landfill site, a composting plant or an incineration plant for subsequent treatment. However, in the garbage compression treatment process of the garbage transfer station, due to the fact that organic compounds (such as proteins, amino acids and the like) containing nitrogen and sulfur in household garbage (especially kitchen garbage) are easy to rot and ferment, malodorous gases such as ammonia gas and hydrogen sulfide can be generated, personal safety of cleaning staff and surrounding residents is seriously threatened, and the garbage transfer station becomes an important environmental protection problem which is needed to be solved urgently and is related to people in the life.
At present, aiming at the air pollution problem, the purification technologies such as photocatalysis, adsorption, low-temperature plasma oxidation and the like are generally adopted, wherein the photocatalysis technology has strong oxidative decomposition capability, can overcome the problems that the adsorption purification technology is easy to saturate, the low-temperature plasma oxidation technology has secondary pollution and the like, and is widely focused by people in the field of air purification.
The photocatalysis technology mainly utilizes a semiconductor material to generate electron transition under the excitation of illumination to form photo-generated electrons and holes, and the photo-generated electrons and holes are captured by water or oxygen adsorbed on the surface of the semiconductor material to generate active groups such as hydroxyl free radicals, superoxide free radicals and the like, so that the active groups are utilized to decompose organic pollutants in the environment. However, tiO is currently being studied and used in a relatively wide range 2 The photocatalytic material can only respond to ultraviolet light to generate electron transition, and the long-term irradiation of the ultraviolet lamp can generate secondary pollution such as ozone. At the same time, a single TiO 2 The semiconductor also has the problems of easy recombination of photo-generated carriers, low photo-catalytic quantum efficiency and the like. At present, researchers mainly adopt means such as doping, noble metal deposition, semiconductor compounding, dye sensitization and the like to perform the treatment on TiO 2 And (5) modifying. Wherein, the nitrogen is doped with TiO 2 Visible light catalytic materials have achieved productionBut there is still a need for further improvement in photogenerated carrier separation and quantum efficiency. In addition, the existing nano photocatalytic material is mainly applied by adding photocatalytic nano particles into polymer film forming materials such as resin, cellulose and the like, and finally loading the polymer film forming materials onto the surface of a substrate to prepare a photocatalytic coating. However, the coating effect of the polymer film former on the photocatalytic nanoparticles may cause a decrease in photocatalytic activity. The precursor sol or nano particles of the photocatalytic material are directly used for forming the film, and subsequent high-temperature heat treatment (generally higher than 350 ℃) is often needed to crystallize the precursor or firmly bond the nano particles to the surface of the substrate, which limits the use of some thermolabile polymer substrates.
Therefore, development of a nano photocatalytic material having both visible light response characteristics and excellent photo-generated carrier separation ability and a high-efficiency loading technique thereof are urgently required.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a preparation method of a ternary purification material for garbage odor treatment.
In order to solve the technical problems, the invention adopts the following solutions:
the preparation method of the ternary purification material for garbage odor treatment comprises the following steps:
(1) 1-5 parts by mass of polyvinylpyrrolidone is dissolved in 5-10 parts by mass of organic solvent, and then 8-15 parts by mass of bismuth salt precursor is added into the solution under magnetic stirring; stirring for 1 hour, and standing at room temperature for 12 hours to obtain a homogeneous spinning solution for electrostatic spinning;
preparing fibers by adopting an electrostatic spinning device, and calcining the prepared fibers at the temperature of 400-550 ℃ at the heating rate of 1 ℃/min for 1-5 h; grinding the calcined product for 3-6 hours by a ball mill to obtain Bi 2 O 3 A nano short fiber;
(2) A graphite rod is adopted as an electrode, the graphite rod is placed in continuously stirred ultrapure water, and voltage of 15-30V is applied to two ends of the electrode through a direct current power supply for 72-120 h; then placing the obtained black turbid electrolyte in an oven at 80 ℃ for drying to obtain black powder; adding the black powder into ethanol according to the mass fraction of 5%, oscillating and dispersing for 2h under 20KHz ultrasonic wave, and centrifuging for 5-30 min at the speed of 8000 rpm; taking supernatant, centrifuging for 10-45 min at 10000rpm, and taking supernatant to obtain nano carbon dot ethanol dispersion;
(3) 1 part by mass of Bi 2 O 3 Adding the nano short fibers into 5-10 parts by mass of nano carbon dot ethanol dispersion liquid, and stirring for 1-5 hours at the speed of 50 rpm; then adding 10-15 parts by mass of deionized water, and adjusting the pH value of the mixed solution to 3-5 by using an acid catalyst; dissolving 1-3 parts by mass of titanium-containing precursor in 3-5 parts by mass of absolute ethyl alcohol, dripping the titanium-containing precursor into the mixed solution under the stirring of water bath at 80 ℃, reacting for 24-48 hours, and filtering; dispersing the filtered product into absolute ethyl alcohol according to the mass fraction of 20% -40% to obtain TiO 2 @C@Bi 2 O 3 Ethanol dispersion of the composite material;
(4) Spraying UV transparent paint on the front and back surfaces of the filter screen by adopting a spraying process, and after standing for 10min, spraying TiO on the front and back surfaces of the filter screen 2 @C@Bi 2 O 3 Ethanol dispersion of the composite material; drying at 60 ℃ for 30min, vertically placing the mixture in an ultraviolet curing device with 500W high-pressure mercury lamps at two sides, keeping the plane of a filter screen at 20cm away from a lamp tube, and turning on the high-pressure mercury lamps to irradiate for 30-60 s to obtain the ternary purifying material for garbage odor treatment.
As a preferable mode of the present invention, the organic solvent in the step (1) is at least one of propylene glycol methyl ether, dimethyl sulfoxide and dimethylformamide.
As a preferable mode of the invention, the bismuth salt precursor in the step (1) is at least one of bismuth nitrate, bismuth sulfate and bismuth chloride.
As a preferred scheme of the invention, the electrostatic spinning device in the step (1) consists of a high-voltage generator, an injection pump and a fiber receiver; and controlling during electrostatic spinning: the voltage is 10-30 kV, the extrusion rate is 0.1-2 ml/h, and the receiving distance is 10-30 cm.
As a preferable mode of the present invention, the acid catalyst in the step (3) is at least one of hydrochloric acid, nitric acid and glacial acetic acid.
As a preferable scheme of the invention, the titanium-containing precursor in the step (3) is at least one of butyl titanate, titanium isopropoxide and titanium tetrachloride.
As a preferable mode of the present invention, when the ethanol solution of the titanium-containing precursor is added dropwise in the step (3), the dropping speed is controlled to be 3ml/min.
As a preferable scheme of the invention, the filter screen in the step (4) is one of a nylon coarse filter screen, a foaming polyurethane filter screen and a stainless steel filter screen.
As a preferred embodiment of the present invention, the preparation method of the UV transparent coating in the step (4) is as follows:
10 to 15 parts by mass of hydrophilic acrylate monomer, 6 to 8 parts by mass of aliphatic polyurethane acrylate monomer, 3 to 5 parts by mass of vinyl ether monomer, 2 to 4 parts by mass of 2-hydroxy-2-methyl-phenyl acetone and 20 to 30 parts by mass of absolute ethyl alcohol are mixed and stirred uniformly.
As a preferable scheme of the invention, the hydrophilic acrylate monomer is at least one of methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate and ethoxylated bisphenol A diacrylate; the functionality of the aliphatic polyurethane acrylate monomer is 7-9; the vinyl ether monomer is at least one of hydroxybutyl vinyl ether, triethylene glycol divinyl ether and 1, 4-cyclohexyl dimethanol divinyl ether.
The implementation principle of the invention is as follows:
the malodor generated by the household garbage in the garbage transfer station comprises a plurality of types of gases, and the malodor gas such as ammonia gas, hydrogen sulfide and the like is mainly used as a main purification treatment object in the invention and the embodiment. By loading nano carbon dots to Bi 2 O 3 Preparation of C@Bi on surface of nano short fiber 2 O 3 Composite material and then TiO is realized by controlling the hydrolysis of the titanium-containing precursor 2 Nanocrystalline at C@Bi 2 O 3 In-situ growth of composite material surface to utilize narrow band gap Bi 2 O 3 The nano short fiber absorbs visible light. Such nano-staple fibers are retained as much as possibleThe high activity characteristic of the nano particles, and the problem of agglomeration of the nano particles is effectively avoided by virtue of the fact that the nano particles are in a micron scale in the axial direction of the fiber, so that the dispersibility in a solvent is improved. The invention utilizes the nano carbon dots to improve TiO 2 With Bi 2 O 3 The photo-generated carrier migration capability between the two layers and further enhance the absorption of visible light, thereby constructing efficient TiO 2 @C@Bi 2 O 3 Ternary composite photocatalytic material.
When the catalytic material is specifically applied, the two-step method is adopted to prepare the photocatalytic coating, a layer of transparent wet film with ultraviolet light curing activity is firstly sprayed on a filter screen substrate, and then TiO is coated 2 @C@Bi 2 O 3 Spraying the composite material onto the surface of the transparent wet film, and finally, curing the transparent wet film by ultraviolet irradiation to obtain TiO (titanium dioxide) 2 @C@Bi 2 O 3 The composite material is fixed on the surface of the coating, so that the photocatalytic coating is prepared on the surface of the filter screen.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention constructs the efficient TiO 2 @C@Bi 2 O 3 Ternary composite photocatalytic material system, compared with nitrogen-doped TiO 2 、Bi 2 O 3 、TiO 2 @Bi 2 O 3 The ternary composite photocatalytic material has higher visible light catalytic activity.
2. The preparation process of the photocatalytic coating by the two-step method solves the problem of photocatalytic performance degradation caused by the coating effect of the polymer film forming matters on the photocatalytic nano particles in the traditional method, and the photocatalytic material is mainly positioned on the surface of the coating where the photocatalytic reaction occurs, and no photocatalytic material exists in the coating, so that the waste of the photocatalytic material is avoided.
3. The invention prepares Bi through electrostatic spinning and ball milling process 2 O 3 The nanometer short fiber effectively avoids the agglomeration problem of the nanometer material in the application process, and improves the uniformity of the distribution of the photocatalysis material on the surface of the coating.
Detailed Description
The invention is described in further detail below in connection with specific embodiments:
the preparation method of the ternary purification material for garbage odor treatment comprises the following steps:
(1) 1-5 parts by mass of polyvinylpyrrolidone is dissolved in 5-10 parts by mass of at least one organic solvent of propylene glycol methyl ether, dimethyl sulfoxide and dimethylformamide, then 8-15 parts by mass of at least one bismuth salt precursor of bismuth nitrate, bismuth sulfate and bismuth chloride is added into the solution under magnetic stirring, and after stirring for 1 hour, the solution is left to stand for 12 hours at room temperature, so that a homogeneous spinning solution for electrostatic spinning is obtained.
Preparing fibers by adopting an electrostatic spinning device, wherein the electrostatic spinning device consists of a high-voltage generator, an injection pump and a fiber receiver; during electrostatic spinning, the control is as follows: the voltage is 10-30 kV, the extrusion rate is 0.1-2 ml/h, and the receiving distance is 10-30 cm. Calcining the prepared fiber at 400-550 ℃ for 1-5 h at a heating rate of 1 ℃/min, grinding the obtained product for 3-6 h by a ball mill, and preparing Bi 2 O 3 A nano short fiber.
(2) Graphite rod is used as electrode, and is placed in continuously stirred ultrapure water, and voltage of 15-30V is applied to two ends of the electrode through a direct current power supply for 72-120 h. Then, placing the obtained black turbid electrolyte in an oven at 80 ℃ for drying to obtain black powder; adding the black powder into ethanol according to the mass fraction of 5%, oscillating and dispersing for 2h under 20KHz ultrasonic wave, and centrifuging for 5-30 min at the speed of 8000 rpm; taking supernatant, centrifuging at 10000rpm for 10-45 min, and taking supernatant to obtain nano carbon dot ethanol dispersion.
(3) 1 part by mass of Bi obtained in the step (1) 2 O 3 Adding the nano short fibers into 5-10 parts by mass of the nano carbon dot ethanol dispersion liquid obtained in the step (2), stirring for 1-5 hours at the speed of 50rpm, then adding 10-15 parts by mass of deionized water, and adjusting the pH value of the mixed liquid to 3-5 by using at least one acid catalyst selected from hydrochloric acid, nitric acid and glacial acetic acid. Then 1 to 3 mass parts of at least one titanium-containing precursor of butyl titanate, titanium isopropoxide and titanium tetrachloride is dissolved in 3 to 5 mass parts of no-titanium precursorAdding the mixture into ethanol water, dripping the mixture into the mixture at the speed of 3ml/min under the stirring of water bath at 80 ℃, filtering after reacting for 24-48 hours, and dispersing the filtered product into absolute ethanol according to the mass fraction of 20-40 percent to obtain TiO 2 @C@Bi 2 O 3 Ethanol dispersion of the composite material.
(4) Spraying UV transparent paint on the front and back surfaces of one filter screen of a nylon coarse filter screen, a foaming polyurethane filter screen and a stainless steel filter screen by adopting a spraying process, and spraying TiO obtained in the step (3) on the front and back surfaces of the filter screen after standing for 10min 2 @C@Bi 2 O 3 And (3) drying the composite material ethanol dispersion liquid at 60 ℃ for 30min, vertically placing the composite material ethanol dispersion liquid in an ultraviolet curing device with 500W high-pressure mercury lamps at two sides, keeping the plane of a filter screen at 20cm from a lamp tube, and turning on the high-pressure mercury lamps to irradiate for 30-60 s to obtain the ternary purification material for garbage odor treatment.
The preparation method of the UV transparent coating comprises the following steps:
10 to 15 parts by mass of at least one hydrophilic acrylate monomer selected from methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate and ethoxylated bisphenol A diacrylate, 6 to 8 parts by mass of aliphatic polyurethane acrylate monomer with the functionality of 7 to 9, 3 to 5 parts by mass of at least one vinyl ether monomer selected from hydroxybutyl vinyl ether, triethylene glycol divinyl ether and 1, 4-cyclohexyl dimethyl alcohol divinyl ether, 2 to 4 parts by mass of 2-hydroxy-2-methyl-phenyl acetone and 20 to 30 parts by mass of absolute ethyl alcohol are mixed and stirred uniformly.
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way. The waste odor treatment ternary cleaning materials were successfully prepared by 8 examples, respectively, and the test data in each example are shown in Table 1 below.
Table 1 example data table
The method for testing the photocatalytic purification performance of the ternary purification material comprises the following steps:
(1) Test materials and devices
Ternary purification material with the size of 45cm multiplied by 45 cm; the size is 60cm multiplied by 80cm, and a fan for blowing downwards and two 24W LED white light sources are arranged at the top of the glove box; a gas injector; GX-6000 gas detector was developed in Japan.
(2) Test procedure
(1) The ternary purification material is filled into a glove box, and leans against the inner wall of the glove box at an angle of 60 degrees with the bottom surface of the glove box, the glove box is closed, and a certain amount of target gas is injected into the glove box by adopting a gas injector, so that the initial concentration of the target gas in the glove box is kept to a certain value a 0 (about 200ppm of ammonia gas and about 50ppm of hydrogen sulfide).
(2) Turning on a light source and a fan, performing photocatalytic reaction for 2 hours, and testing the concentration a of target gas in the glove box t The method comprises the steps of carrying out a first treatment on the surface of the The target gas removal rate P can be calculated by the following formula, so that the photocatalytic purification performance of the ternary purification material is characterized.
Compared with the existing photocatalytic material, the method has the following conditions:
under the same test conditions, the photocatalytic material of the prior art: (1) Bi (Bi) 2 O 3 The ammonia removal rate of (2) was 71.7% and the hydrogen sulfide removal rate was 69.1%; (2) Nitrogen doped TiO 2 The ammonia removal rate of (2) is 74.7%, and the hydrogen sulfide removal rate is 68.5%; (3) TiO (titanium dioxide) 2 @Bi 2 O 3 The ammonia removal rate of (a) was 83.4%, and the hydrogen sulfide removal rate was 81.6%.
It can be seen that in this way,TiO prepared in examples of the present invention 2 @C@Bi 2 O 3 The visible light catalytic performance of the composite material is superior to that of the above material (the data are shown in the tail part of table 1).
Finally, it should also be noted that the above list is merely a specific example of the invention. Obviously, the invention is not limited to the above embodiment examples, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (7)
1. The preparation method of the ternary purification material for garbage odor treatment is characterized by comprising the following steps of:
(1) Dissolving 1-5 parts by mass of polyvinylpyrrolidone in 5-10 parts by mass of an organic solvent, and then adding 8-15 parts by mass of bismuth salt precursor into the solution under magnetic stirring; stirring for 1 hour, and standing at room temperature for 12 hours to obtain a homogeneous spinning solution for electrostatic spinning; the bismuth salt precursor is at least one of bismuth nitrate, bismuth sulfate and bismuth chloride;
preparing fibers by adopting an electrostatic spinning device, and calcining the prepared fibers at the temperature of 400-550 ℃ at the heating rate of 1 ℃/min for 1-5 h; grinding the calcined product for 3-6 hours by a ball mill to obtain Bi 2 O 3 A nano short fiber;
(2) A graphite rod is adopted as an electrode, the graphite rod is placed in continuously stirred ultrapure water, and a voltage of 15-30V is applied to two ends of the electrode through a direct current power supply for 72-120 hours; then placing the obtained black turbid electrolyte in an oven at 80 ℃ for drying to obtain black powder; adding the black powder into ethanol according to the mass fraction of 5%, oscillating and dispersing for 2h under 20KHz ultrasonic wave, and centrifuging for 5-30 min at the speed of 8000 rpm; taking supernatant, centrifuging at a speed of 10000rpm for 10-45 min, and taking supernatant to obtain nano carbon dot ethanol dispersion;
(3) 1 part by mass of Bi 2 O 3 Adding the nano short fibers into 5-10 parts by mass of nano carbon dot ethanol dispersion liquid, and stirring for 1-5 hours at the speed of 50 rpm; then adding 10-15 parts by mass of deionized waterAdjusting the pH value of the mixed solution to 3-5 by using an acid catalyst; dissolving 1-3 parts by mass of a titanium-containing precursor in 3-5 parts by mass of absolute ethyl alcohol, dropwise adding the titanium-containing precursor into the mixed solution under water bath stirring at 80 ℃, reacting for 24-48 hours, and filtering; dispersing the filtered product into absolute ethyl alcohol according to the mass fraction of 20% -40% to obtain TiO 2 @C@Bi 2 O 3 Ethanol dispersion of the composite material;
the acid catalyst is at least one of hydrochloric acid, nitric acid and glacial acetic acid, and the titanium-containing precursor is at least one of butyl titanate, titanium isopropoxide and titanium tetrachloride;
(4) Spraying UV transparent paint on the front and back surfaces of the filter screen by adopting a spraying process, and after standing for 10min, spraying TiO on the front and back surfaces of the filter screen 2 @C@Bi 2 O 3 Ethanol dispersion of the composite material; and (3) drying at 60 ℃ for 30min, vertically placing the mixture in an ultraviolet curing device with 500W high-pressure mercury lamps at two sides, keeping the plane of a filter screen at 20cm away from the lamp tube, and turning on the high-pressure mercury lamps to irradiate for 30-60 s to obtain the ternary purifying material for garbage odor treatment.
2. The method according to claim 1, wherein the organic solvent in step (1) is at least one of propylene glycol methyl ether, dimethyl sulfoxide, and dimethylformamide.
3. The method of claim 1, wherein the electrospinning apparatus in step (1) consists of a high voltage generator, a syringe pump and a fiber receiver; and controlling during electrostatic spinning: the voltage is 10-30 kV, the extrusion rate is 0.1-2 ml/h, and the receiving distance is 10-30 cm.
4. The method according to claim 1, wherein the dropping speed is controlled to be 3ml/min when the ethanol solution of the titanium-containing precursor is dropped in the step (3).
5. The method of claim 1, wherein the filter in step (4) is one of a nylon coarse filter, a foamed polyurethane filter, and a stainless steel filter.
6. The method according to claim 1, wherein the UV transparent coating in step (4) is prepared by the following method:
10-15 parts by mass of hydrophilic acrylate monomer, 6-8 parts by mass of aliphatic polyurethane acrylate monomer, 3-5 parts by mass of vinyl ether monomer, 2-4 parts by mass of 2-hydroxy-2-methyl-phenyl acetone and 20-30 parts by mass of absolute ethyl alcohol are mixed and stirred uniformly.
7. The method of claim 6, wherein the hydrophilic acrylate monomer is at least one of methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, ethoxylated bisphenol a diacrylate; the functionality of the aliphatic polyurethane acrylate monomer is 7-9; the vinyl ether monomer is at least one of hydroxybutyl vinyl ether, triethylene glycol divinyl ether and 1, 4-cyclohexyl dimethanol divinyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111645229.7A CN114289007B (en) | 2021-12-30 | 2021-12-30 | Preparation method of ternary purification material for garbage odor treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111645229.7A CN114289007B (en) | 2021-12-30 | 2021-12-30 | Preparation method of ternary purification material for garbage odor treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114289007A CN114289007A (en) | 2022-04-08 |
| CN114289007B true CN114289007B (en) | 2023-12-29 |
Family
ID=80970870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111645229.7A Active CN114289007B (en) | 2021-12-30 | 2021-12-30 | Preparation method of ternary purification material for garbage odor treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114289007B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745377A (en) * | 2009-10-12 | 2010-06-23 | 天津大学 | Method for preparing visible light photocatalyst Bi2O3/TiO |
| WO2017091815A1 (en) * | 2015-11-25 | 2017-06-01 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
| CN107497428A (en) * | 2017-08-28 | 2017-12-22 | 中山大学 | A kind of TiO of more shell nanoparticles2Photochemical catalyst and preparation method and application |
| CN108033437A (en) * | 2017-12-08 | 2018-05-15 | 中国矿业大学 | A kind of quick method for preparing carbon dots of salt auxiliary |
| CN110801809A (en) * | 2019-11-09 | 2020-02-18 | 浙江大学 | Preparation method of porous visible light catalytic composite material with high adsorption capacity |
| CN111185152A (en) * | 2020-01-14 | 2020-05-22 | 北京工业大学 | Multifunctional coupled PAC/Bi2O3/TiO2Method for preparing composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11161094B2 (en) * | 2019-05-01 | 2021-11-02 | Imam Abdulrahman Bin Faisal University | Titania-carbon dot-reduced graphene oxide composites, their make, and use |
-
2021
- 2021-12-30 CN CN202111645229.7A patent/CN114289007B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745377A (en) * | 2009-10-12 | 2010-06-23 | 天津大学 | Method for preparing visible light photocatalyst Bi2O3/TiO |
| WO2017091815A1 (en) * | 2015-11-25 | 2017-06-01 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
| CN107497428A (en) * | 2017-08-28 | 2017-12-22 | 中山大学 | A kind of TiO of more shell nanoparticles2Photochemical catalyst and preparation method and application |
| CN108033437A (en) * | 2017-12-08 | 2018-05-15 | 中国矿业大学 | A kind of quick method for preparing carbon dots of salt auxiliary |
| CN110801809A (en) * | 2019-11-09 | 2020-02-18 | 浙江大学 | Preparation method of porous visible light catalytic composite material with high adsorption capacity |
| CN111185152A (en) * | 2020-01-14 | 2020-05-22 | 北京工业大学 | Multifunctional coupled PAC/Bi2O3/TiO2Method for preparing composite material |
Non-Patent Citations (2)
| Title |
|---|
| α-Bi2O3纳米纤维的制备及其光催化性能研究;杨帆;《西安理工大学学报》;第34卷;422-427 * |
| 荧光纳米碳点的合成及其催化应用研究;李海涛;《中国优秀博士学位论文全文数据库 工程科技I辑》(第5期);B014-18 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114289007A (en) | 2022-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| CN103990485B (en) | Azotized carbon nano particle modifies composite bismuth vanadium photocatalyst and preparation method thereof | |
| CN109569684B (en) | Plasma modified metal oxide and g-carbon nitride co-modified titanium dioxide nanorod composite photocatalyst as well as preparation method and application thereof | |
| CN103285861B (en) | An Ag3VO4/TiO2 compound nano-wire having visible light activity, a preparation method and applications thereof | |
| CN102205236B (en) | Method for preparing carbon-doped titanium dioxide composite material and application thereof | |
| CN107952464B (en) | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system | |
| CN107983353B (en) | TiO 22-Fe2O3Preparation method and application of composite powder | |
| CN109174075A (en) | A kind of rare-earth element modified titanium dioxide nano photocatalysis material and preparation method thereof for photocatalytic degradation VOCs | |
| CN102527396A (en) | Preparation method and application method of high-efficiency codoped compound photocatalyst | |
| CN113908855B (en) | Preparation method of supported porous photocatalytic fiber membrane | |
| CN110201688B (en) | Preparation and control method of catalytic electrode for bioelectrochemistry and photoelectrocatalysis degradation of ethyl acetate and toluene gas | |
| CN113617366A (en) | Material for degrading organic pollutants in wastewater | |
| CN109201029B (en) | Preparation method of efficient porous composite photocatalytic material | |
| CN114289007B (en) | Preparation method of ternary purification material for garbage odor treatment | |
| US11896960B1 (en) | High-efficiency visible-light catalytic material and preparation method and application thereof | |
| CN109046308A (en) | A kind of graphene micro-flowers/nano zinc oxide photocatalysis material and preparation method thereof | |
| CN113546625A (en) | Electrostatic spinning defective TiO2/Fe3O4Composite nanofiber material and preparation method thereof | |
| CN112371102A (en) | Nano photocatalytic composite material compounded by RGO and rare earth doped titanium dioxide, preparation method and air purification application | |
| CN108940343B (en) | Fe-TiO2nanotube/g-C3N4Composite material and preparation method and application thereof | |
| CN109331852B (en) | Photocatalyst catalyst material and preparation method and application thereof | |
| CN109999792A (en) | A kind of porous ZnWO4/WO3Nano pipe light catalyst and simple controllable preparation method | |
| CN1846850A (en) | Fibrous nanometer catalyst material excited with natural light and its prepn process | |
| CN115430420A (en) | Preparation method of antibacterial and photocatalytic dual-functional environmental purification fiber membrane, product and application thereof | |
| CN113351246A (en) | Preparation method of salicylaldehyde-sensitized nano titanium dioxide photocatalyst | |
| CN112961551A (en) | Titanium dioxide catalytic air purification coating and preparation method and application thereof |
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 |