CN109465015A - A kind of photochemical catalyst and preparation method thereof handling organic sewage - Google Patents
A kind of photochemical catalyst and preparation method thereof handling organic sewage Download PDFInfo
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- CN109465015A CN109465015A CN201811288806.XA CN201811288806A CN109465015A CN 109465015 A CN109465015 A CN 109465015A CN 201811288806 A CN201811288806 A CN 201811288806A CN 109465015 A CN109465015 A CN 109465015A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000010865 sewage Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 12
- 239000001119 stannous chloride Substances 0.000 claims abstract description 12
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000011265 semifinished product Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 2
- 235000015170 shellfish Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010949 copper Substances 0.000 abstract description 10
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 230000002165 photosensitisation Effects 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000002156 mixing Methods 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
- 230000003287 optical effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- 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
- 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
-
- 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
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of photochemical catalysts and preparation method thereof for handling organic sewage, it is prepared from the following raw materials in parts by weight: 100-150 parts of fatty acid methyl ester ethoxylate sodium sulfonate, 200-250 parts of stannous chloride powder, 200-250 parts of shell carrier, 2-5 parts of chloroplatinic acid, compared to the ultraviolet light that titanium dioxide can only be less than 388nm using wavelength, the present invention can directly be less than the sunlight of 650nm using wavelength, the utilization scope to solar energy has been widened significantly, copper and shell it is from a wealth of sources, it is cheap and easy to get, preparation is simple, production cost is low, carrier made of shell does not have an impact the photosensitizing effect of photochemical catalyst substantially, improve the catalytic activity of photochemical catalyst.
Description
Technical field
The present invention relates to sewage treatment field, especially a kind of photochemical catalyst and preparation method thereof for handling organic sewage.
Background technique
In China, annual quantity of wastewater effluent has reached 40,000,000,000 tons, has the section of half organic in national seven big water systems
Object or heavy metal pollution, and organic pollutant not only exists that the time is long, range is wide, but also handles difficult.Traditional sewage treatment
Method has physical method, chemical method and bioanalysis, but determines that these three processing methods are answered actual the characteristics of organic pollutant
All there is certain difficulty and limitation in.Physical method is the object that is enriched with and transfers the pollution；Organic pollutant is mostly difficult oxidation
Substance, chemical method are generally difficult to its exhaustive oxidation be easy to causeing secondary pollution；Bioanalysis is suitable for biochemical organic matter, right
Artificial synthesized organic matter is generally difficult to degrade.Therefore, photocatalysis oxidation technique is because its reaction condition is simple, reaction is thorough, suitable
It is extensively concerned with property, there is great application prospect.
The principle of photocatalysis oxidation technique be photochemical catalyst under the irradiation of ultraviolet light, internal electron migration, generate hole
And electronics, since electronics has reproducibility, and hole has the extremely strong ability for obtaining electronics, can be by the OH in water-And H2O points
Son is oxidized to the hydroxyl radical free radical (OH) with extremely strong oxidisability, so that redox reaction occurs, it will be difficult to degrade in water
Organic matter is completely degraded into H2O and CO2.Reaction condition is mild, can carry out under normal temperature and pressure；Without adding any oxidant, keep away
Further chemical contamination is exempted from, and has reduced costs；Photocatalysis oxidation reaction is thorough, and reaction product is thoroughly converted into CO2、H2O
With acid, inorganic salts etc.；Applicability is wide, is a kind of wide spectrum method for treating water, it was reported that photocatalytic oxidation is to the dirt more than 3000 kinds
Contaminate water (such as dyeing waste water, eutrophication sanitary sewage, oil extraction-generated waste water, pesticide, classes of herbicides removal and for water body detoxify)
Processing have good result.
Titanium dioxide is most common photochemical catalyst, it have optical activity is strong, nontoxic, light is stable, under room temperature not
The advantages that being soluble in soda acid, but the broadband taboo degree of titanium dioxide is about 3.2eV, i.e., only wavelength is less than the ultraviolet light of 388nm
Can just titanium dioxide be made to excite, therefore when in use, need the artificial light sources such as high-pressure sodium lamp, black light lamp, ultraviolet germicidal, and people
After work light source power consumption is big, at high cost, service life is short, lacks economy, and titanium dioxide is fixed in carrier, surface area
It reduces, will lead to the reduction of its catalytic activity.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention, which provides a kind of pair of ultraviolet light and visible light, good photoresponse
Handle the photochemical catalyst and preparation method thereof of organic sewage.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of photochemical catalyst handling organic sewage, the photochemical catalyst are prepared from the following raw materials in parts by weight: fatty acid methyl
100-150 parts of ester ethoxylate sodium sulfonate (FMES), 200-250 parts of stannous chloride powder (CuCl), shell powder 200-250
Part and chloroplatinic acid (H2PtCl6) 2-5 parts.
The method for preparing the photochemical catalyst includes that steps are as follows:
1) fatty acid methyl ester ethoxylate sodium sulfonate is added in the sodium chloride solution of concentration 2.5mol/L, stirs 15 points
Clock is kept stirring under state, is homogeneously added into stannous chloride powder, is continued stirring 15 minutes, is kept stirring under state, and shellfish is added
Shell carrier stirs 40 minutes, next filters, and solid is placed in ultrasonic oscillation in deionized water and cleans 10 minutes, distilled water punching
Wash 3 times, 65 DEG C drying 7 hours, semi-finished product A is made；
This step chemical reaction equation is as follows:
CuCl+H2O+CaO→Ca2++CuOH+Cl-
CuOH→Cu2O+H2O
The main ingredient activity CaO of shell powder provides binding site in situ for the Basic fluxing raction of CuCl, and CuCl is dissolved in NaCl solution
Complex liquid is formed, reaction generates nanometer CuO H under alkaline environment, but since nanometer CuO H is difficult to be stabilized, dehydration life
At nanometer Cu2O。
Reaction generates nanometer Cu2O size is small, large specific surface area, and surface lacks the atom of neighbouring coordination, thus has very
High activity, this leads to a nanometer Cu2O easily reunites, and is unfavorable for it and plays distinctive photo absorption property, therefore is made with shell powder
It is fixed for carrier.
Due to nanometer Cu2The characteristic that O easily reunites passes through addition sodium chloride solution and fatty acid methyl ester ethoxylate sulphur
Sour sodium forms stable decentralized system.The effect of sodium chloride solution has two: first is that forming complex liquid with stannous chloride；Second is that conduct
Deflocculant, sodium ion and chloride ion make a nanometer Cu2The diffusion of O electric double layer is made by the coulomb repulsion effect between electric double layer
The resultant force reunited between particle substantially reduces, to realize the purpose of nano particle dispersion.And fatty acid methyl ester ethyoxyl
Compound sodium sulfonate belongs to yin-non-amphoteric surfactant, 18 carbonic acid of the fatty acid methyl ester as macromolecule, molecular chain length and has
Branch has splendid dispersion force, and lime soap dispersing power is up to 310ppm, and common anionic surfactant dodecyl
The dispersion of calcium soap of benzene sulfonic acid sodium salt is only 98ppm, and neopelex has and easily divides intolerant to hard water and excessive concentration
The defect of layer, solubility is inferior to fatty acid methyl ester ethoxylate sodium sulfonate, therefore fatty acid methyl ester ethoxylate in cold water
Sodium sulfonate can make a nanometer Cu as most preferably dispersing agent2O uniformly and stably exists in the solution and remains nanoparticle
State.Again by constantly stirring in preparation process, make a nanometer Cu2O is highly dispersed in medium system, increases the total boundary of system
Face prevents from reuniting, to make a nanometer Cu2O is uniformly covered with carrier surface.
The nanometer Cu prepared using the method2There is ideal original position to match between O and shell carrier, material can be significantly improved
The bonding state of middle two-phase interface makes material have excellent thermodynamic stability；Secondly, In-situ reaction eliminates the second phase
Pre-synthesis simplifies technique, reduces the cost of raw material；In addition, In-situ reaction can also realize the special microstructure of material
Property is designed and obtained, while avoiding the second phase being likely encountered when preparing material because of traditional handicraft dispersion uneven, boundary
Face combine it is insecure and because physics, chemical reaction so that constituent is mutually lost pre-designed performance the deficiencies of the problem of.
2) chloroplatinic acid is added in pure water and is uniformly mixed, pure water dosage and semi-finished product A are isometric, add semi-finished product A
It impregnates 1 hour after mixing evenly, is then rapidly added the sodium borohydride solution isometric with semi-finished product A, concentration 0.1mol/L,
30min is stirred at 1000r/min and obtains suspension, and suspension stirs at 100 DEG C and is evaporated to anhydrous to anhydrous, gained sample
It is placed in 80 DEG C of baking oven to dry 2 hours, can be prepared by the photochemical catalyst.
The reactive chemistry formula of this step is as follows:
NaBH4+2H2PtCl6+ 12NaOH=2Pt+12NaCl+NaB (OH)4+8H2O
Chloroplatinic acid is restored by sodium borohydride solution, by impregnating and stirring evaporation operation, by simple substance platinum uniform load in carrier,
A nanometer Cu is made2O-Pt/ shell composite photo-catalyst, the effect of simple substance platinum are load modification photochemical catalysts, improve photochemical catalyst
Optical response range.Referring to Fig.1, the present invention has the absorption of Qiang Erkuan, main photosensitive work in ultraviolet light and visible light region
Property ingredient be nanometer Cu2O, nanometer Cu2The forbidden bandwidth of O is about 2.0-2.2eV, directly can be less than 650nm too using wavelength
Sunlight has greatly widened photochemical catalyst to the utilization scope of solar energy.
The method for preparing the shell powder comprises the steps of:
1) hydrochloric acid solution that concentration is 0.2mol/L impregnates shell 20 minutes, and shell can be completely covered in hydrochloric acid dosage, connect down
Shell is taken out, distilled water flushing 3 times, 120 degree of drying box dry 1 hour, take out, obtain by pretreated shell；
2) in being put into described in Muffle furnace by pretreated shell, 850 DEG C temperature lower calcination 2.5 hours, take out shell
Grinding, sieves with 100 mesh sieve, and obtains the shell carrier.
It is the organic substance and inorganic substances in order to remove shell surface with salt acid soak shell, is conducive to a nanometer Cu2O with
The attachment of simple substance platinum.High-temperature calcination is passed through in order to which the main composition-calcium carbonate in shell is completely decomposed into active calcium oxide
The shell powder of processing is a kind of excellent carrier, have many advantages, such as large specific surface area, suction-operated it is strong, it is from a wealth of sources be easy to get, and
And the shell powder carrier by processing is to Cu2The photosensitizing effect of O does not have an impact substantially, referring to Fig.1, photochemical catalyst and simple
Nano cuprous oxide compare, the maximum difference of absorption coefficient is no more than 0.03, and it is sub- thus to illustrate that carrier has little influence on oxidation
The photosensitizing effect of copper, and shell powder made of 850 DEG C of temperature lower calcinations has strongest photocatalytic activity.Reactive chemistry formula
It is as follows:
CaCO3+ high temperature → CaO+CO2
The beneficial effects of the present invention are: can only be less than the ultraviolet light of 388nm using wavelength compared to titanium dioxide, the present invention can be straight
The sunlight for being less than 650nm using wavelength is connect, has widened the utilization scope to solar energy significantly；The source of copper and shell is wide
It is general, cheap and easy to get, preparation is simple, production cost is low；Carrier made of shell does not generate the photosensitizing effect of photochemical catalyst substantially
It influences, improves the catalytic activity of photochemical catalyst.
Detailed description of the invention
Fig. 1 is the ultraviolet-visible light diffusing reflection absorption spectroanalysis figure of the present invention and nano cuprous oxide.
Specific embodiment
Below with reference to examples illustrate the present invention and analysis.
Embodiment 1:
Photochemical catalyst is prepared from the following raw materials in parts by weight: 100 parts of fatty acid methyl ester ethoxylate sodium sulfonate, stannous chloride
200 parts of powder, 200 parts of shell carrier, 2 parts of chloroplatinic acid.
The method and step for preparing the photochemical catalyst is as follows:
1) sodium chloride for the fatty acid methyl ester ethoxylate sodium sulfonate of above-mentioned parts by weight being added to concentration 2.5mol/L is molten
In liquid, stirs 15 minutes, be kept stirring under state, be homogeneously added into the stannous chloride powder of above-mentioned parts by weight, continue to stir
It 15 minutes, is kept stirring under state, the shell carrier of above-mentioned parts by weight is added, stir 40 minutes, next filter, solid is set
Ultrasonic oscillation cleans 10 minutes in deionized water, distilled water flushing 3 times, 65 DEG C drying 7 hours, obtained semi-finished product A；
2) chloroplatinic acid of above-mentioned parts by weight being added in pure water and is uniformly mixed, pure water dosage and semi-finished product A are isometric, then plus
Enter semi-finished product A to impregnate after mixing evenly 1 hour, is then rapidly added the sodium borohydride solution isometric with semi-finished product A, concentration is
0.1mol/L stirs 30min at 1000r/min and obtains suspension, suspension stirred at 100 DEG C be evaporated to it is anhydrous to nothing
Water, gained sample are placed in 80 DEG C of baking oven and dry 2 hours, can be prepared by the photochemical catalyst.
The method and step for preparing the shell carrier is as follows:
1) hydrochloric acid solution that concentration is 0.2mol/L impregnates shell 20 minutes, and shell can be completely covered in hydrochloric acid dosage, connect down
Shell is taken out, distilled water flushing 3 times, 120 degree of drying box dry 1 hour, take out, obtain by pretreated shell；
2) in being put into described in Muffle furnace by pretreated shell, 850 DEG C temperature lower calcination 2.5 hours, take out shell
Grinding, sieves with 100 mesh sieve, and obtains the shell carrier.
Embodiment 2:
Photochemical catalyst is prepared from the following raw materials in parts by weight: 150 parts of fatty acid methyl ester ethoxylate sodium sulfonate, stannous chloride
250 parts of powder, 250 parts of shell carrier, 5 parts of chloroplatinic acid.
The method for preparing photochemical catalyst and shell carrier is same as Example 1.
Embodiment 3:
Photochemical catalyst is prepared from the following raw materials in parts by weight: 125 parts of fatty acid methyl ester ethoxylate sodium sulfonate, stannous chloride
225 parts of powder, 225 parts of shell carrier, 3 parts of chloroplatinic acid.
The method for preparing photochemical catalyst and shell carrier is same as Example 1.
Embodiment 4:
Photochemical catalyst is prepared from the following raw materials in parts by weight: 100 parts of fatty acid methyl ester ethoxylate sodium sulfonate, stannous chloride
200 parts of powder, 250 parts of shell powder, 4 parts of chloroplatinic acid.
The method for preparing photochemical catalyst and shell carrier is same as Example 1.
Embodiment 5:
Photochemical catalyst is prepared from the following raw materials in parts by weight: 150 parts of fatty acid methyl ester ethoxylate sodium sulfonate, stannous chloride
250 parts of powder, shell powder 200,2 parts of chloroplatinic acid.
The method for preparing photochemical catalyst and shell carrier is same as Example 1.
Using the sewage of sewage treatment plant as experimental water, sewage volume 500mL, 28 DEG C of outdoor temperature, test period is
12 noon is at 3 points in afternoon.PH value is measured using pH meter, and suspended matter (SS) is measured with transmissometer, and COD (COD) is with micro-
Wave clears up instrument measurement, and the experimental result of 5 embodiments is as follows:
| Testing index | PH value | SS(mg/L) | COD(mg/L) |
| Sewage sample | 8.2 | 160 | 930 |
| Embodiment 1 | 7.6 | 2.2 | 10 |
| Embodiment 2 | 7.1 | 1.9 | 9.5 |
| Embodiment 3 | 7.5 | 1.9 | 12 |
| Embodiment 4 | 7.1 | 2.1 | 10 |
| Embodiment 5 | 7.3 | 2.2 | 9 |
5 embodiments are effectively handled the organic pollutant in sewage from the experimental results, and SS value and COD value are big
Amplitude decline.A standard in the primary standard of national sewage comprehensive emission standard: COD≤50mg/L, SS≤10mg/L, pH value 6
~9, meet discharge standard by the sewage of photocatalyst treatment.
The preparation step and experimental procedure of the photochemical catalyst unless stated otherwise, are not so grasped at normal temperatures and pressures
Make.
Above embodiment cannot limit the protection scope of the invention, and the personnel of professional skill field are not departing from
In the case where the invention general idea, the impartial modification and variation done still fall within the range that the invention is covered
Within.
Claims (3)
1. it is a kind of handle organic sewage photochemical catalyst, it is characterised in that the photochemical catalyst by following parts by weight raw material system
At: 100-150 parts of fatty acid methyl ester ethoxylate sodium sulfonate, 200-250 parts of stannous chloride powder, shell carrier 200-250
Part and chloroplatinic acid 2-5 parts.
2. a kind of prepare the method for handling the photochemical catalyst of organic sewage described in claim 1, it is characterised in that steps are as follows:
1) fatty acid methyl ester ethoxylate sodium sulfonate is added in the sodium chloride solution of concentration 2.5mol/L, stirs 15 points
Clock is kept stirring under state, is homogeneously added into stannous chloride powder, is continued stirring 15 minutes, is kept stirring under state, and shellfish is added
Shell carrier stirs 40 minutes, next filters, and solid is placed in ultrasonic oscillation in deionized water and cleans 10 minutes, distilled water punching
Wash 3 times, 65 DEG C drying 7 hours, semi-finished product A is made；
2) chloroplatinic acid is added in pure water and is uniformly mixed, pure water dosage and semi-finished product A are isometric, add semi-finished product A stirring
Dipping 1 hour, is then rapidly added the sodium borohydride solution isometric with semi-finished product A after uniformly, concentration 0.1mol/L,
30 min are stirred under 1000 r/min and obtain suspension, and suspension stirs at 100 DEG C and is evaporated to anhydrous to anhydrous, gained sample
It is placed in 80 DEG C of baking oven to dry 2 hours, can be prepared by the photochemical catalyst.
3. the photochemical catalyst of processing organic sewage according to claim 1 or claim 2, it is characterised in that prepare the shell carrier
Method and step is as follows:
1) hydrochloric acid solution that concentration is 0.2mol/L impregnates shell 20 minutes, and shell can be completely covered in hydrochloric acid dosage, connect down
Shell is taken out, distilled water flushing 3 times, 120 degree of drying box dry 1 hour, take out, obtain by pretreated shell；
2) in being put into described in Muffle furnace by pretreated shell, 850 DEG C temperature lower calcination 2.5 hours, take out shell
Grinding, sieves with 100 mesh sieve, and obtains the shell carrier.
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| CN113332981A (en) * | 2021-06-15 | 2021-09-03 | 华东理工大学 | Carbon dioxide reduction photocatalytic material, preparation method and application thereof |
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