CN102513093A - High-concentration salt-containing wastewater liquid phase oxidation catalyst, preparation method thereof and treatment method - Google Patents
High-concentration salt-containing wastewater liquid phase oxidation catalyst, preparation method thereof and treatment method Download PDFInfo
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- CN102513093A CN102513093A CN2011103920191A CN201110392019A CN102513093A CN 102513093 A CN102513093 A CN 102513093A CN 2011103920191 A CN2011103920191 A CN 2011103920191A CN 201110392019 A CN201110392019 A CN 201110392019A CN 102513093 A CN102513093 A CN 102513093A
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Abstract
The invention discloses a titanium-silicon composite oxide catalyst for high-concentration salt-containing wastewater liquid phase oxidation treatment. The titanium-silicon composite oxide catalyst is characterized by comprising the following substances in percentage by mass: 10-70% of titanium dioxide, 10-60% of silicon dioxide, 1-20% of chromium oxide and 1-20% of light rare earth oxide. The invention also discloses a preparation method of the titanium-silicon composite oxide catalyst and a high-concentration salt-containing wastewater liquid phase oxidation treatment method by utilizing the catalyst. The catalyst without adding precious metals can be used for high-concentration salt-containing virulent wastewater liquid phase oxidation treatment. When being used, the catalyst is almost not lost, is long in service life, good in COD (Chemical Oxygen Demand) removal effect, low in price and capable of achieving a good effect.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of high concentration brine waste liquid-phase oxidation catalyst; The invention still further relates to the preparation method of this high concentration brine waste liquid-phase oxidation catalyst; The invention still further relates to and use the processing method that this catalyst carries out the high concentration brine waste.
Background technology
The chemical wastewater treatment of high concentration, saliferous is perplexing the synthetic industry of chemical industry always.Owing to do not have reasonable method to handle these hypertoxic waste water in the prior art, caused especially Domestic Environment disaster of the whole world.
Nippon Shokubai Co., Ltd discloses a kind of catalyst that contains precious metal cobalt, nickel, silver, gold, platinum, palladium, rhodium, iridium, ruthenium, has obtained very good effect.Too but costliness and catalyst are prone to run off this catalyst cost, the life-span is short, are difficult to implement in China, referring to CN1045398C.
It also is to contain precious metal catalyst that Chinese patent document CN1197781C and CN 1068564C have announced a kind of, and just content reduces.The vanadic anhydride that adds simultaneously more is prone to run off.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, provides a kind of and forms rationally, do not add the high concentration brine waste liquid-phase oxidation catalyst that precious metal also can reach very good effect.
Another technical problem to be solved by this invention has provided the method for making of aforesaid high concentration brine waste liquid-phase oxidation catalyst.
Another technical problem to be solved by this invention has provided a kind of processing method that above-mentioned catalyst carries out the high concentration brine waste of using.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is that a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and be characterized in: it is made up of the material of following quality percentage composition,
Titanium dioxide 10～70%;
Silica 1 0～60%;
Chrome green 1～20%;
Oxidation light rare earth 1～20%.
Oxidation light rare earth of the present invention can obtain through following method:
With the aqueous solution of cerium, lanthanum light rare earth chloride, with soda ash or sodium hydrate aqueous solution neutralization, the mixed sediment of generation is aqua oxidation light rare earth REO
2NH
2O obtains oxidation light rare earth REO through the calcining oven dry
2Wherein, RE is cerium and lanthanum, and n is a positive integer.
In above-described titanium-Si composite oxide catalyst technology scheme: the preferred mass percentage composition of each material consists of:
Titanium dioxide 30～55%;
Silica 30～50%;
Chrome green 5～15%;
Oxidation light rare earth 5～15%.
In above-described titanium-Si composite oxide catalyst:
Described titanium dioxide preferably comes from metatitanic acid, titanyl sulfate hydrolysate, titanium chloride hydrolysate;
Described silica preferably comes from Ludox;
Described chrome green preferably comes from chromic anhybride glucose or sucrose reduzate chromium hydroxide.
Titanium of the present invention-Si composite oxide catalyst can be by the preparation of prior art conventional method, preferably by following method preparation.A kind of like the described titanium of above technical scheme-Si composite oxide Preparation of catalysts method, its step is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 4～10mm, length 4～12mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 500～600 ℃ of calcinings, promptly get again; Catalytic component after the calcining meets claim 1 or 2 described material and percentage by weights thereof.
The invention also discloses a kind of high concentration brine waste liquid phase oxidation processing method, be characterized in, this method is used the described titanium of above technical scheme-Si composite oxide catalyst, the titanium that perhaps above-described preparation method makes-Si composite oxide catalyst; Its step is following:
(1) loads titanium-Si composite oxide catalyst in the accumulation fixed bed;
(2) with compression pump waste water is full of the accumulation fixed bed, begins to heat up; Bed temperature is stabilized in 220～320 ℃;
(3) advance oxygen, with pressure stability at 3.0～12.0MPa; Pile up fixed bed generation catalytic oxidation, waste water acutely heats up, and through heating fluid temperature is shifted out;
(4) system stability is at 220～320 ℃ of temperature, pressure 3.0～12.0MPa, and pump advances waste water and oxygen continuously; The liquid air speed per hour of waste water is at 0.5～3h
-1The fixed bed outlet is equipped with pressure valve and is set in 8.0MPa, reacts the gas-liquid mixture that finishes and presses to flash column automatically, removes small organic molecule, and this steam gets into anaerobic pond; Direct discharging of waste water after up to standard or advance anaerobic pond.
In the technical scheme of above-described high concentration brine waste liquid phase oxidation processing method, during processing: the fixing bed tempertaure of piling up is preferably 260～280 ℃; Pressure is preferably 6.0～8.0MPa.
In the technical scheme of above-described high concentration brine waste liquid phase oxidation processing method, the interior lining panel of described accumulation fixed bed is preferably pure nickel plate or Ha Shi B plate.
Compared with prior art, catalyst of the present invention need not add precious metal such as cobalt, nickel, silver, gold, platinum, palladium, rhodium, iridium, ruthenium, copper, and the exhausted water phase oxidation that can be used for high concentration, saliferous, severe toxicity is handled.Catalyst runs off hardly during use, long service life, and the COD removal effect is good, and is cheap, also can reach very good effect.
The specific embodiment
Below further describe concrete technical scheme of the present invention,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1, and a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is made up of the material of following quality percentage composition,
Titanium dioxide 45%; Silica 25%;
Chrome green 10%; Oxidation light rare earth 20%.
The preparation of employing conventional method.
Embodiment 2, and a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is made up of the material of following quality percentage composition,
Titanium dioxide 10%; Silica 60%;
Chrome green 20%; Oxidation light rare earth 10%;
Its preparation methods steps is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 40mm, length 4mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 500 ℃ of calcinings, promptly get again; The material of the catalytic component after the calcining and percentage by weight thereof are as stated.
Embodiment 3, and a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is made up of the material of following quality percentage composition,
Titanium dioxide 70%; Silica 1 0%;
Chrome green 1%; Oxidation light rare earth 19%;
Its preparation methods steps is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 10mm, length 12mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 600 ℃ of calcinings, promptly get again; The material of the catalytic component after the calcining and percentage by weight thereof are as stated.
Embodiment 4, and a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is made up of the material of following quality percentage composition,
Titanium dioxide 30%;
Silica 50%;
Chrome green 5%;
Oxidation light rare earth 15%;
Its preparation methods steps is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 6mm, length 8mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 550 ℃ of calcinings, promptly get again; The material of the catalytic component after the calcining and percentage by weight thereof are as stated.
Embodiment 5, and a kind of high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is made up of the material of following quality percentage composition,
Titanium dioxide 55%;
Silica 30%;
Chrome green 10%;
Oxidation light rare earth 5%.
Embodiment 6, and in any one described titanium-Si composite oxide catalyst of embodiment 1-5: described titanium dioxide comes from metatitanic acid, titanyl sulfate hydrolysate, titanium chloride hydrolysate;
Described silica comes from Ludox;
Described chrome green comes from chromic anhybride glucose or sucrose reduzate chromium hydroxide.
Its preparation methods steps is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 4～10mm, length 4～12mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 500～600 ℃ of calcinings, promptly get again; Catalytic component after the calcining meets claim 1 or 2 described material and percentage by weights thereof.
Embodiment 7, and a kind of high concentration brine waste liquid phase oxidation processing method, this method are used any one described titanium-Si composite oxide catalyst of embodiment 1-6, and its step is following:
(1) loads titanium-Si composite oxide catalyst in the accumulation fixed bed;
(2) with compression pump waste water is full of the accumulation fixed bed, begins to heat up; Bed temperature is stabilized in 220 ℃;
(3) advance oxygen, with pressure stability at 3.0MPa; Pile up fixed bed generation catalytic oxidation, waste water acutely heats up, and through heating fluid temperature is shifted out;
(4) system stability is at 220 ℃ of temperature, pressure 3.0MPa, and pump advances waste water and oxygen continuously; The liquid air speed per hour of waste water is at 0.5h
-1The fixed bed outlet is equipped with pressure valve and is set in 8.0MPa, reacts the gas-liquid mixture that finishes and presses to flash column automatically, removes small organic molecule, and this steam gets into anaerobic pond; Direct discharging of waste water after up to standard or advance anaerobic pond.
Embodiment 8, and a kind of high concentration brine waste liquid phase oxidation processing method, this method are used any one described titanium-Si composite oxide catalyst of embodiment 1-6, and its step is following:
(1) loads titanium-Si composite oxide catalyst in the accumulation fixed bed;
(2) with compression pump waste water is full of the accumulation fixed bed, begins to heat up; Bed temperature is stabilized in 320 ℃;
(3) advance oxygen, with pressure stability at 12.0MPa; Pile up fixed bed generation catalytic oxidation, waste water acutely heats up, and through heating fluid temperature is shifted out;
(4) system stability is at 320 ℃ of temperature, pressure 12.0MPa, and pump advances waste water and oxygen continuously; The liquid air speed per hour of waste water is at 3h
-1The fixed bed outlet is equipped with pressure valve and is set in 8.0MPa, reacts the gas-liquid mixture that finishes and presses to flash column automatically, removes small organic molecule, and this steam gets into anaerobic pond; Direct discharging of waste water after up to standard or advance anaerobic pond.
Embodiment 9, and a kind of high concentration brine waste liquid phase oxidation processing method, this method are used any one described titanium-Si composite oxide catalyst of embodiment 1-6, and its step is following:
(1) loads titanium-Si composite oxide catalyst in the accumulation fixed bed;
(2) with compression pump waste water is full of the accumulation fixed bed, begins to heat up; Bed temperature is stabilized in 280 ℃;
(3) advance oxygen, with pressure stability at 7.0MPa; Pile up fixed bed generation catalytic oxidation, waste water acutely heats up, and through heating fluid temperature is shifted out;
(4) system stability is at 270 ℃ of temperature, pressure 7.0MPa, and pump advances waste water and oxygen continuously; The liquid air speed per hour of waste water is at 2h
-1The fixed bed outlet is equipped with pressure valve and is set in 8.0MPa, reacts the gas-liquid mixture that finishes and presses to flash column automatically, removes small organic molecule, and this steam gets into anaerobic pond; Direct discharging of waste water after up to standard or advance anaerobic pond.
Embodiment 10, and in embodiment 7 or the 8 or 9 described high concentration brine waste liquid phase oxidation processing methods: the interior lining panel of described accumulation fixed bed is pure nickel plate or Ha Shi B plate.
Embodiment 11, and the liquid phase oxidation of high concentration brine waste is handled with titanium-Si composite oxide catalyst applications experiment one.
(1) adopts catalyst experiment of the present invention
1, catalytic component:
| Chemical constituent | Cr 2O 3 | REO | TiO 2 | SiO 2 |
| Content, % (m/m) | 8 | 8 | 34 | 50 |
2, Oxybenzene experiment:
Preparation waste water: 1% benzene aqueous dispersion (stir and do not stop);
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Benzene detects in the water outlet: 0% (gas chromatography), but the aldehyde and the carboxylic acid of small-molecular weight are arranged;
Metal detection in the water outlet: Cr does not detect, and Ti does not detect (atomic absorption method);
Conclusion: benzene complete oxidation.
3, oxidation normal octane experiment:
Preparation waste water: 1% normal octane aqueous dispersion (stir and do not stop);
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Normal octane detects in the water outlet: 0%;
Conclusion: normal octane complete oxidation.
4, cacodyl oxide sulfoxide experiment:
Preparation waste water: the 1% methyl-sulfoxide aqueous solution;
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Methyl-sulfoxide detects in the water outlet: 0% (gas chromatography) has sulfur dioxide;
Conclusion: methyl-sulfoxide complete oxidation.
5, oxidation 2-methylpyrazine experiment:
Preparation waste water: the 1%2-methylpyrazine aqueous solution;
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
The 2-methylpyrazine detects in the water outlet: 0% (gas chromatography);
Conclusion: 2-methylpyrazine complete oxidation.
6, pyridine oxide experiment:
Preparation waste water: 1% pyridine solution;
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Pyridine detects in the water outlet: 0.45% (gas chromatography);
Conclusion: the pyridine oxidation is incomplete, oxidation Decomposition rate 55%.
7, oxidation ammoniacal liquor experiment:
Preparation waste water: 1% ammonia spirit;
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Ammonia detects in the water outlet: 1%;
Conclusion: to ammonia non-oxidation ability.
(2) control experiment
1, catalytic component:
| Chemical constituent | Cr 2O 3 | REO | TiO 2 | SiO 2 |
| Content, % (m/m) | —— | —— | 50 | 50 |
2, Oxybenzene experiment
Preparation waste water: 1% benzene aqueous dispersion (stir and do not stop);
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Benzene detects in the water outlet: 0.11% (gas chromatography).But aldehyde and carboxylic acid that small-molecular weight is arranged;
Conclusion: the benzene oxidation is incomplete, oxidation Decomposition rate 89%.
Embodiment 12, and the liquid phase oxidation of high concentration brine waste is handled with titanium-Si composite oxide catalyst applications experiment two.
1, catalytic component:
| Chemical constituent | Cr 2O 3 | REO | TiO 2 | SiO 2 |
| Content, % (m/m) | 10 | 10 | 30 | 50 |
2, Oxybenzene experiment:
Preparation waste water: 1% benzene aqueous dispersion (stir and do not stop);
Condition: 275～280 ℃ of temperature, pressure 7.0～8.0MPa;
Liquid air speed per hour 1 h
-1
Benzene detects in the water outlet: 0% (gas chromatography).But aldehyde and carboxylic acid that small-molecular weight is arranged;
Conclusion: benzene complete oxidation.
Embodiment 13, adopt embodiment 11 described high concentration brine waste liquid phase oxidations to handle and carry out batch production application experiment one with titanium-Si composite oxide catalyst.
Wastewater source and character: insecticide factory, pyridine, bipyridyl, paraquat product waste water.COD=60000, salt (in sodium chloride) mass concentration 15%, dark brown has lamination.The result is following:
Oxidation heat liberation, byproduct steam with respect to former heavy oil incinerating method, is handled waste water per ton and is practiced thrift 980 yuan of costs, and economic effect is fairly obvious.
Embodiment 13, adopt embodiment 11 described high concentration brine waste liquid phase oxidations to handle and carry out batch production application experiment two with titanium-Si composite oxide catalyst.
Wastewater source and character: insecticide factory, the herbicide product contains methyl-sulfoxide waste water.COD=75000, salt (in sodium chloride) mass concentration 5%, dark brown.The result is following:
| Temperature | 275～280℃ |
| Pressure | 7.0～8.0MPa； |
| The liquid air speed per hour | 1 h -1 |
| Full condensation water outlet COD | 900ppm＃ |
| Water outlet COD after the flash distillation | 320ppm |
| The water outlet outward appearance | Extremely faint yellow |
| Conversion ratio | Conversion ratio=98.8% |
Because water outlet contains sulfur dioxide, the result is higher.
Embodiment 14, adopt embodiment 11 described high concentration brine waste liquid phase oxidations to handle and carry out batch production application experiment three with titanium-Si composite oxide catalyst.
Wastewater source and character: chemical plant, ammoxidation product, waste water contain the tar of toluene and high temperature generation.COD=21000, yellow.The result is following:
| Temperature | 275～280℃ |
| Pressure | 7.0～8.0MPa； |
| The liquid air speed per hour | 1 h -1 |
| Full condensation water outlet COD | 970ppm |
| Water outlet COD after the flash distillation | 440ppm |
| The water outlet outward appearance | Extremely faint yellow |
| Conversion ratio | Conversion ratio=95.4% |
Embodiment 15, adopt embodiment 11 described high concentration brine waste liquid phase oxidations to handle and carry out batch production application experiment four with titanium-Si composite oxide catalyst.
Wastewater source and character: synthetic drug plant, the category-B vitamin products, waste water contains methylnaphthoquinone.COD=45000, salt (in sodium chloride) mass concentration 9%, buff.The result is following:
| Temperature | 275～280℃ |
| Pressure | 7.0～8.0MPa； |
| The liquid air speed per hour | 1 h -1 |
| Full condensation water outlet COD | 930ppm |
| Water outlet COD after the flash distillation | 450ppm |
| The water outlet outward appearance | Extremely faint yellow |
| Conversion ratio | Conversion ratio=97.9% |
Embodiment 16, adopt embodiment 11 described high concentration brine waste liquid phase oxidations to handle and carry out batch production application experiment five with titanium-Si composite oxide catalyst.
Wastewater source and character: synthetic perfume factory, heterocyclic product, waste water contain heterocycle and methyl tertiary butyl ether(MTBE)s such as many methylpyrazines, thiazole.COD=80000, salt (in sodium chloride) mass concentration 0.8%, dark brown.The result is following:
| Temperature | 275～280℃ |
| Pressure | 7.0～8.0MPa； |
| The liquid air speed per hour | 1 h -1 |
| Full condensation water outlet COD | 750ppm |
| Water outlet COD after the flash distillation | 320ppm |
| The water outlet outward appearance | Extremely faint yellow |
| Conversion ratio | Conversion ratio=99.1% |
Claims (7)
1. a high concentration brine waste liquid phase oxidation is handled with titanium-Si composite oxide catalyst, and it is characterized in that: it is made up of the material of following quality percentage composition,
Titanium dioxide 10～70%;
Silica 1 0～60%;
Chrome green 1～20%;
Oxidation light rare earth 1～20%.
2. titanium according to claim 1-Si composite oxide catalyst is characterized in that: it is made up of the material of following quality percentage composition,
Titanium dioxide 30～55%;
Silica 30～50%;
Chrome green 5～15%;
Oxidation light rare earth 5～15%.
3. titanium according to claim 1 and 2-Si composite oxide catalyst is characterized in that:
Described titanium dioxide comes from metatitanic acid, titanyl sulfate hydrolysate, titanium chloride hydrolysate;
Described silica comes from Ludox;
Described chrome green comes from chromic anhybride glucose or sucrose reduzate chromium hydroxide.
4. titanium-Si composite oxide Preparation of catalysts method according to claim 1 or claim 2 is characterized in that its step is following:
(1) blend is mediated: a certain amount of metatitanic acid, chromium hydroxide, aqua oxidation light rare earth and Ludox are mediated in kneader repeatedly, got blend;
(2) extruded moulding: with blend extrusion repeatedly on the screw rod banded extruder, disconnected again bar becomes the cylindrical pellet of diameter 4～10mm, length 4～12mm;
(3) oven dry and calcining: after 120 ℃ of oven dry of cylindrical pellet, 500～600 ℃ of calcinings, promptly get again; Catalytic component after the calcining meets claim 1 or 2 described material and percentage by weights thereof.
5. high concentration brine waste liquid phase oxidation processing method; It is characterized in that; This method is used claim 1 or 2 or 3 described titanium-Si composite oxide catalyst, the titanium-Si composite oxide catalyst that perhaps uses the described preparation method of claim 4 to make; Its step is following:
(1) loads titanium-Si composite oxide catalyst in the accumulation fixed bed;
(2) with compression pump waste water is full of the accumulation fixed bed, begins to heat up; Bed temperature is stabilized in 220～320 ℃;
(3) advance oxygen, with pressure stability at 3.0～12.0MPa; Pile up fixed bed generation catalytic oxidation, waste water acutely heats up, and through heating fluid temperature is shifted out;
(4) system stability is at 220～320 ℃ of temperature, pressure 3.0～12.0MPa, and pump advances waste water and oxygen continuously; The liquid air speed per hour of waste water is at 0.5～3h
-1The fixed bed outlet is equipped with pressure valve and is set in 8.0MPa, reacts the gas-liquid mixture that finishes and presses to flash column automatically, removes small organic molecule, and this steam gets into anaerobic pond; Direct discharging of waste water after up to standard or advance anaerobic pond.
6. high concentration brine waste liquid phase oxidation processing method according to claim 5 is characterized in that, during processing: fixing accumulation bed tempertaure is 260～280 ℃; Pressure is 6.0～8.0MPa.
7. high concentration brine waste liquid phase oxidation processing method according to claim 5 is characterized in that, the interior lining panel of described accumulation fixed bed is pure nickel plate or Ha Shi B plate.
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| CN106477801A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of wastewater from chemical industry oxidation treatment method |
| CN106622209A (en) * | 2016-12-30 | 2017-05-10 | 佛山市国汉科技有限公司 | Photocatalyst powder and preparation method thereof |
| CN106622209B (en) * | 2016-12-30 | 2019-12-31 | 佛山市国汉科技有限公司 | Photocatalyst powder and preparation method thereof |
| CN109574386A (en) * | 2018-12-11 | 2019-04-05 | 安徽三江水务工程有限公司 | A kind for the treatment of of Perfume Wastewater processing system |
| CN109574386B (en) * | 2018-12-11 | 2024-04-16 | 安徽三江水务工程有限公司 | Spice wastewater treatment system |
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