CN109603870B - Preparation and application of bimetal substituted solid heteropolyacid salt composite catalyst - Google Patents
Preparation and application of bimetal substituted solid heteropolyacid salt composite catalyst Download PDFInfo
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- 239000007787 solid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 239000005947 Dimethoate Substances 0.000 claims description 6
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000001782 photodegradation Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 239000002028 Biomass Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000011973 solid acid Substances 0.000 abstract 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A preparation and application of a bimetal substituted solid heteropolyacid salt composite catalyst belong to the field of new energy materials and environmental protection engineering. The invention fully utilizes the light absorption performance and enhanced charge separation efficiency of heteropoly acid in the ultraviolet-visible spectrum range, and prepares a series of bimetallic solid heteropoly acid salt composite catalysts in a mode of replacing heteropoly acid protons with bimetallic salts under hydrothermal conditions. The composite catalyst can be used as a solid acid and a photocatalyst respectively, is used for catalytic conversion of biomass and photocatalytic oxidation degradation of organic pollutants, has the advantages of mild preparation conditions, high catalytic activity and reusability, can be applied to treatment of pesticide wastewater, dye wastewater, phenol wastewater and the like, and provides a new treatment technology for reducing high-concentration organic pollutants in sewage.
Description
Technical Field
The invention belongs to the technical field of environmental protection engineering, and relates to a preparation method of a solid heteropolyacid salt composite catalyst and application thereof in organic pollutant photodegradation.
Background
The photocatalytic degradation technology is a new effective method for reducing the organic matters difficult to degrade in the environment. In semiconductor photocatalysts, titanium dioxide (TiO)2) It is of particular interest because of its high photocatalytic activity, high chemical stability, low toxicity and low cost. However, the high recombination rate of photo-generated electrons and holes results in lower photon efficiency. To eliminate this drawback, researchers have worked on TiO2Many modification studies such as metal ion and non-metal ion doping, co-deposition of metals, and other semiconductor compounding, dye sensitization on the surface of titanium dioxide, and novel titanium dioxide-based composites have been conducted.
In recent years, a great deal of research shows that the construction of a heterojunction photoelectric conversion system can improve the separation capability and the transfer capability of photogenerated electrons and holes, so that the construction of a heterojunction system by compounding binary or multiple semiconductors is one of effective means for improving the solar energy utilization efficiency and the photocatalytic activity. Phosphotungstic acid is a compound having KThe heteropolyacid of eggin type structure has strong ability of accepting electrons and has photochemical characteristics very similar to semiconductor photocatalyst. Lu et al (J Hazard Mater,2012,199-3PW12O40/TiO2The composite membrane photocatalyst has excellent photocatalytic activity on water-soluble dye rhodamine b under xenon lamp irradiation. Juli a n A et al (J Photothiobi A,2014,289:22-30) at high temperatures (a)>Synthesizing phosphotungstic acid and silicotungstic acid modified TiO by a sol-gel method at 400 DEG C2The materials, these composite materials all show higher photocatalytic activity. However, heteropoly acids/TiO have been reported2The composite material has complex preparation process and high energy consumption, and the heteropoly acid is easy to dissolve in water and difficult to reuse. Aiming at the defects of the existing preparation process, the patent provides a novel bimetal substituted solid heteropoly acid salt composite catalyst which is mild in preparation process, high in activity of a composite material and reusable.
Disclosure of Invention
Aiming at the defects of the existing preparation process, the patent provides a novel bimetal substituted solid heteropoly acid salt composite catalyst, and the substituted heteropoly acid has strong electron accepting capability and has photochemical characteristics very similar to semiconductor photocatalysts. Further with TiO2After surface recombination, heteropoly acid anions play a role in modification, thereby capturing TiO2Absorb electrons generated by photons, prolong the recombination time of electron-hole pairs and further improve TiO2Efficiency of nanoparticle photocatalysis. The method adopts a mild hydrothermal method, the composite material has high photocatalytic activity, is suitable for the advanced treatment of various waste water, and can be recycled without generating secondary pollution.
The specific technical scheme is as follows:
a preparation method of a bimetal substituted solid heteropolyacid salt composite catalyst comprises the following steps: dissolving transition metal salt in water to prepare salt solution, and then dropwise adding the salt solution into heteropoly acid aqueous solution or heteropoly acid and TiO2Forming a mixed solution A in the mixed solution, and then dropwise adding the mixed solution AAnd (3) obtaining a mixed solution B from a cesium chloride aqueous solution, wherein the molar ratio of the transition metal salt to the cesium chloride to the heteropoly acid in the mixed solution B is 0.25-1: 1-2: 1, the mixed solution B is a milky suspension, the mixed solution B is transferred into a reaction kettle, hydrothermal treatment is carried out for 1-5 h at 160-220 ℃, and the mixed solution B is filtered, washed and dried to obtain the bimetal substituted solid heteropoly acid salt composite catalyst.
The transition metal salt is one of stannic chloride, nickel chloride, copper chloride, ferric chloride and zinc chloride, and the heteropoly acid is one of phosphotungstic heteropoly acid and silicotungstic heteropoly acid.
Further, when the mixed solution A contains TiO2Then, TiO in the mixed solution B2The molar ratio of the heteropoly acid to the heteropoly acid is 10-100: 1.
The concentration of the heteropoly acid in the mixed solution B is 5-10 g/L.
The application of the bimetal substituted solid heteropolyacid salt composite catalyst prepared by the method comprises the following steps: weighing a bimetal substituted solid heteropolyacid salt composite catalyst, and adding the bimetal substituted solid heteropolyacid salt composite catalyst into a quartz reactor containing an organic pollutant solution, wherein the concentration of the organic pollutant solution is 10-100 mg/L; the dosage of the bimetallic substituted solid heteropolyacid salt composite catalyst in each liter of organic pollutant solution is 0.1-1.5 g; stirring for 0.5h under the dark light condition, then stirring and reacting for 1-5 h under the ultraviolet light, and detecting and calculating the removal rate of the organic pollutants.
The organic pollutant is one of tetracycline antibiotics and dimethoate.
The power of the ultraviolet lamp is 250W, the wavelength is 365nm, and the stirring speed is 50-300 r/min.
The invention has the advantages that the preparation process of the bimetal substituted solid heteropoly acid salt composite catalyst is simple and easy to realize unit standardization operation, and the bimetal solid heteropoly acid salt is nano-particles, has excellent electron accepting capability and photooxidation reaction capability and is combined with TiO2The surface recombination is realized, and the catalyst is stable in the process of photocatalytic reaction, can be recycled and reused, thereby realizing the characteristics of reducing the cost and having no secondary pollution emission.
Drawings
FIG. 1 is an SEM spectrogram of a nano-bimetal substituted solid heteropolyacid salt composite catalyst.
FIG. 2 is an XRD spectrum of the nano-bimetal substituted solid heteropolyacid salt composite catalyst.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example one
Preparation of SnCl4Aqueous solution according to SnCl4Dropwise adding the solution with the molar ratio of 0.25:1 to the phosphotungstic heteropoly acid aqueous solution, then dropwise adding the CsCl solution according to the molar ratio of 1.5:1 of CsCl to the phosphotungstic heteropoly acid to obtain milky suspension, transferring the milky suspension to a reaction kettle, carrying out hydrothermal treatment at 220 ℃ for 1H, filtering, washing and drying to obtain the nano composite catalyst H0.5Sn0.25Cs1.5PW12O40。
Preparing 10mg/L tetracycline aqueous solution, adding H0.5Sn0.25Cs1.5PW12O40The working concentration is 0.75g/L, stirring is carried out for 0.5h under the condition of dark light, then stirring is carried out for reaction for 2.5h under the ultraviolet light of 250W and 365nm, and the tetracycline removal rate is 93.3 percent.
Example two
Preparation of SnCl4Aqueous solution according to SnCl4Dropwise adding the solution with the molar ratio of 0.25:1 to the phosphotungstic heteropoly acid aqueous solution, then dropwise adding the CsCl solution according to the molar ratio of 1:1 of CsCl to the phosphotungstic heteropoly acid to obtain milky suspension, transferring the milky suspension to a reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 5 hours, filtering, washing and drying to obtain the nano composite catalyst HSn0.25CsPW12O40。
Preparing 50mg/L tetracycline aqueous solution, adding HSn0.25CsPW12O40The working concentration is 0.1g/L, stirring is carried out for 0.5h under the condition of dark light, then stirring is carried out for reaction for 5h under the ultraviolet light of 250W and 365nm, and the tetracycline removal rate is 79%.
EXAMPLE III
Preparation of SnCl4Aqueous solution according to SnCl4Dropwise adding the mixed solution with phosphotungstic heteropoly acid in a molar ratio of 0.25:1To phosphotungstic heteropoly acid and TiO2In suspension in which phosphotungstic heteropoly acid and TiO2The molar ratio of the CsCl to the phosphotungstic acid is 1:100, then CsCl solution is dripped according to the molar ratio of the CsCl to the phosphotungstic acid of 1:1 to obtain milky suspension, the milky suspension is transferred to a reaction kettle and is hydrothermally treated for 2 hours at 200 ℃, and then the suspension is filtered, washed and dried to obtain the nano composite catalyst HSn0.25CsPW12O40/TiO2The SEM spectrum is shown in figure 1, and the XRD spectrum is shown in figure 2.
Preparing 15mg/L dimethoate aqueous solution, adding HSn0.25CsPW12O40The working concentration is 1g/L, stirring is carried out for 0.5h under the condition of dark light, then stirring is carried out for reaction for 2h under the ultraviolet light of 250W and 365nm, and the dimethoate removal rate is 93%.
Example four
Preparing NiCl2Aqueous solution, according to NiCl2The mol ratio of the silicon-tungsten heteropoly acid and the TiO is 1:12In suspension in a solution of silicotungstic heteropoly acid and TiO2The molar ratio of the CsCl to the silicotungstic heteropoly acid is 1:10, then CsCl solution is dripped according to the molar ratio of the CsCl to the silicotungstic heteropoly acid of 1:1 to obtain milky suspension, the milky suspension is transferred to a reaction kettle and is hydrothermally treated for 2 hours at 200 ℃, and the nano composite catalyst NiCSPW is obtained after filtration, washing and drying12O40/TiO2。
Preparing 15mg/L dimethoate aqueous solution, adding NiCSPW12O40/TiO2The working concentration is 1g/L, stirring is carried out for 0.5h under the condition of dark light, then stirring is carried out for reaction for 2h under the ultraviolet light of 250W and 365nm, and the dimethoate removal rate is 89%.
Claims (5)
1. A preparation method of a bimetal substituted solid heteropolyacid salt composite catalyst is characterized by comprising the following steps:
dissolving transition metal salt in water to prepare salt solution, and then dropwise adding the salt solution to heteropoly acid and TiO2The mixed solution A is formed, a cesium chloride aqueous solution is dripped into the mixed solution A to obtain a mixed solution B, the molar ratio of the transition metal salt, the cesium chloride and the heteropoly acid in the mixed solution B is 0.25-1: 1-2: 1, and the mixed solution B is milky white suspensionTransferring the turbid liquid into a reaction kettle, carrying out hydrothermal treatment for 1-5 h at 160-220 ℃, filtering, washing and drying to obtain a bimetal substituted solid heteropolyacid salt composite catalyst for organic pollutant photodegradation;
the transition metal salt is one of stannic chloride, nickel chloride, copper chloride, ferric chloride and zinc chloride, and the heteropoly acid is one of phosphotungstic heteropoly acid and silicotungstic heteropoly acid;
TiO in the mixed solution B2The molar ratio of the heteropoly acid to the heteropoly acid is 10-100: 1.
2. The preparation method of the bimetallic substituted solid heteropolyacid salt composite catalyst according to claim 1, wherein the concentration of the heteropolyacid in the mixed solution B is 5-10 g/L.
3. Use of a bimetallic-substituted solid heteropolyacid salt composite catalyst prepared by the method as claimed in claim 1 or 2, characterized by comprising the steps of:
weighing a bimetal substituted solid heteropolyacid salt composite catalyst, and adding the bimetal substituted solid heteropolyacid salt composite catalyst into a quartz reactor containing an organic pollutant solution, wherein the concentration of the organic pollutant solution is 10-100 mg/L; the dosage of the bimetallic substituted solid heteropolyacid salt composite catalyst in each liter of organic pollutant solution is 0.1-1.5 g; stirring for 0.5h under the dark light condition, then stirring and reacting for 1-5 h under the ultraviolet light, and detecting and calculating the removal rate of the organic pollutants.
4. The use of the bimetallic-substituted solid heteropolyacid salt composite catalyst according to claim 3, wherein the organic contaminant is one of tetracycline antibiotics and dimethoate.
5. The application of the bimetal substituted solid heteropolyacid salt composite catalyst according to claim 4, wherein the ultraviolet lamp power is 250W, the wavelength is 365nm, and the stirring speed is 50-300 r/min.
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| CN109603870A (en) | 2019-04-12 |
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