CN110330153A - N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method - Google Patents
N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method Download PDFInfo
- Publication number
- CN110330153A CN110330153A CN201910632465.1A CN201910632465A CN110330153A CN 110330153 A CN110330153 A CN 110330153A CN 201910632465 A CN201910632465 A CN 201910632465A CN 110330153 A CN110330153 A CN 110330153A
- Authority
- CN
- China
- Prior art keywords
- waste water
- plate
- pidolidone
- hydrogen peroxide
- processing method
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing methods, belong to the technical field of pharmacy wastewater treatment.Processing method includes one: adjusting pH: the pH of raw wastewater being adjusted to 2-6, obtains waste water A；Two: Fenton oxidation: adding the mixture or aqueous hydrogen peroxide solution of water-soluble ferrous salt and aqueous hydrogen peroxide solution into waste water A, obtain waste water B, be separated by solid-liquid separation, and obtains waste water B supernatant；Three: coagulating sedimentation: the pH of waste water B being adjusted to 7.5-9, flocculant is added, obtains flocculation sedimentation and waste water C；Four: electrocatalytic oxidation: waste water C being passed through to electrocatalytic oxidation system, is purified water after water outlet.The present invention realizes the processing of waste water, and qualified discharge.
Description
Technical field
The present invention relates to the technical field of pharmacy wastewater treatment, in particular to a kind of N- p-benzoyl-Pidolidone
Pharmaceutical intermediate wastewater processing method.
Background technique
Industrial wastewater includes production waste water, production waste and cooling water, refer to the waste water generated in industrial processes and
Waste liquid, wherein containing the pollution generated in industrial production materials, intermediate product, byproduct and the production process outflowed with water
Object, many kinds of, complicated component.
In industrial wastewater, chemical raw material quantity is big, type is more due to using for chemical industry, and what is be discharged in production process is useless
Water also just has quantity big, complicated component, containing the feature more than hazardous substance.And the pharmaceuticals industry in chemical industry, raw material at
The various feature of point complicated, production process multiplicity, product category, and the Wastewater Pollutant content generated in pharmacy procedure it is high, can
Biodegradability is poor, water quality and quantity changes greatly, is one of industrial wastewater difficult to deal with.
N- p-benzoyl-Pidolidone is a kind of medicine intermediate, can be used for the production of methopterin and folic acid.N-
When p-benzoyl-Pidolidone preparation, p-nitrophenyl formyl paddy is first condensed to yield by paranitrobenzoyl chloride and glutamic acid
Propylhomoserin, then restored p-nitrophenyl carbamylglutamic by iron powder, N- p-benzoyl-Pidolidone can be obtained.
N- p-benzoyl-Pidolidone production waste water COD is up to 10000mg/L, and coloration is up to 1000 times, is high
COD, the acid waste water of high chroma.The preparation process of more N- p-benzoyl-Pidolidones or folic acid in the prior art,
The wastewater treatment method being related to is seldom.
Summary of the invention
The purpose of the present invention is to provide a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing sides
Method reaches grade III Standard and the local garden sewage discharge for handling waste water and meeting in " integrated wastewater discharge standard "
Standard.
Above-mentioned technical purpose of the invention has the technical scheme that
Kind N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, which comprises the following steps:
One: adjusting pH: the pH of raw wastewater being adjusted to 2-6, obtains waste water A；
Two: the mixture or aquae hydrogenii dioxidi of water-soluble ferrous salt and aqueous hydrogen peroxide solution Fenton oxidation: are added into waste water A
Solution obtains waste water B, is separated by solid-liquid separation, and obtains waste water B supernatant；
Three: coagulating sedimentation: the pH of waste water B being adjusted to 7.5-9, flocculant is added, obtains flocculation sedimentation and waste water C；
Four: electrocatalytic oxidation: waste water C being passed through to electrocatalytic oxidation system, is purified water after water outlet；
The electrocatalytic oxidation system is two-dimentional electrocatalysis device；
The mass concentration of hydrogen peroxide is 10%-30% in the aqueous hydrogen peroxide solution.
By adopting the above technical scheme, p-nitrophenyl formyl is contained in N- p-benzoyl-Pidolidone acid waste water
Chlorine, glutamic acid, the organic impurities based on p-nitrophenyl carbamylglutamic, and a large amount of ferrous ions and part iron ion.To nitre
Base chlorobenzoyl chloride is dissolved in ether, meets water and alcohol decomposes, the easy moisture absorption, density is greater than water；Contain hydroxyl in glutamate molecule, is slightly soluble in
Water.
In the Fenton oxidation of two steps, the ferrous ion in water-soluble ferrous salt can be urged aqueous hydrogen peroxide solution
Change, promote the generation of hydroxyl radical free radical, hydroxyl radical free radical has very high electronegativity or electrophilicity, can be without in selective oxidation water
Most of organic matters.Hydroxy radical attacks glutamic acid, so that glucose oxidation is decomposed, generates carbon dioxide, water, and contain ammonia
The organic molecule of base, and under acidic environment, amino can continue by hydrogen peroxide oxidation into nitro；Nitro is hydrophobic group,
It is changed into precipitating and and water stratification.Paranitrobenzoyl chloride meet water decomposition, generate paranitrobenzoic acid, p-nitrophenyl formamide or
Ethyl p-nitrobenzoate and hydrogen chloride, hydrogen chloride, which is dissolved in the water, provides acidic environment, and remaining product is converted into precipitating.
Due in Fenton's reaction, needing to guarantee the free property of ferrous ion and ferrous ion, so setting 2- for pH
6, it prevents ferrous ion and ferrous ion to be converted into precipitating under alkaline condition, guarantees the trip of ferrous ion and ferrous ion
Amorph.Meanwhile the experiment proved that, the precipitating occurred in this step is relatively stable in acid condition, can be separated；And
Under alkaline condition, extraordinary hydrophily can be shown, water is adsorbed in glar, so that precipitating and water can not carry out just
Often separation, so that wastewater treatment can not carry out.Fenton's reaction in the prior art, typically add aqueous hydrogen peroxide solution and
After ferrous ion, between waste water is adjusted to alkalinity, by iron cement and organic matter glar coprecipitation, but uncomfortable in the waste water
With；So in this application, first clearing out organic matter precipitating, then iron cement is removed in three steps, guarantee that organic matter is heavy
Shallow lake mud can be separated from waste water.
In three step coagulating sedimentation, using alkaline condition and flocculant, by the ferrous ion in waste water B, iron ion, two steps
Remaining organic matter and suspended solid (SS) are precipitated and are flocculated in rapid, obtain the sediment of large volume and filtering.It carries out
The ending of Fenton and the purified treatment of second level.
In the electrocatalytic oxidation of four steps, two-dimentional electrocatalysis device is used, catalytic and oxidative electrolysis technology is the one of advanced oxidation
Kind of form, refers under electric field action, generates to anode surface high-performance great amount of hydroxy group free radical, in ecosystem oxygen and solution
Oxidation reaction occurs for pollutant.Under the action of electric field, hydrone discharges the hydroxy radical of generation on the anode surface, and hydroxyl is free
The electrophilic attack of base has pollutant, forms small molecule inorganic matter, so that it is innoxious to realize waste water.
In summary waste water treatment process, waste water are discharged the three-level reached in " integrated wastewater discharge standard " after treatment
Standard (GB8978-1996), and local garden sewage drainage standard (COD≤350mg/L, ammonia nitrogen≤35mg/L).
Further preferably are as follows: in two step, the mass parts ratio of hydrogen peroxide and COD are 1:(0.05-0.5), when
When the molal weight of waste water A ferrous ions and hydrogen peroxide ratio is greater than 0.1:1, hydrogen peroxide is added into waste water A；Work as waste water
When the molal weight of A ferrous ions and hydrogen peroxide ratio is less than 0.1:1, aqueous hydrogen peroxide solution and water are added into waste water A
Dissolubility ferrous salt, the molal weight of waste water B ferrous ions and the molal weight ratio of hydrogen peroxide are (0.1-1): 1.
By adopting the above technical scheme, it during producing N- p-benzoyl-Pidolidone, needs to be obtained with iron powder reducing
It arrives, so a large amount of ferrous ion can be contained in waste water, and ferrous ion is precisely the catalyst of hydrogen peroxide in Fenton's reaction, institute
To be fit closely using Fenton's reaction, it is possible to reduce the cost input of ferrous salt.And in order to guarantee in waste water ferrous iron from
The content of son is enough, carries out Concentration Testing to the ferrous ion in waste water before Fenton's reaction, to obtain ferrous in waste water
The total moles quality of ion；The COD content in waste water is measured again, the dosage of hydrogen peroxide is calculated according to COD total amount, finally
It determines the need for adding ferrous ion salt, does not all need to add under normal circumstances.
Further preferably are as follows: during two step, pH is controlled between 2.5~4.
By adopting the above technical scheme, the hydroxy radical that Fenton's reaction generates under the conditions of the pH is most active, and processing COD effect is most
Obviously.
Further preferably are as follows: in three step, pH is adjusted to by 7.5-9 by alkali tune agent, the alkali tune agent is quality
Sodium hydroxide solution that score is 5-30%, mass fraction are 5-25% sodium carbonate liquor, mass fraction is 5-25% bicarbonate
One of sodium solution is a variety of.
By adopting the above technical scheme, alkali tune agent has selected the solution for dissolving completion in advance, is that solid is added in order to prevent
It generates heat after waste water, the stability in entire wastewater treatment process is had an impact, while fever may be such that fractions
It evaporates and generates exhaust gas；On the other hand, solution may be implemented to pump and measure, and be more convenient the operation of automation.
Further preferably are as follows: the electrocatalytic oxidation system is three-dimensional electrocatalysis device and two-dimentional electrocatalysis device, waste water C
Sequentially enter three-dimensional electrocatalysis device and two-dimentional electrocatalysis device.
By adopting the above technical scheme, three-dimensional electro-catalytic oxidation technology (TDE), also known as granule electrode are a kind of novel electricity
Chemical reactor.Its key is exactly granular working electrode material to be loaded between the electrode of conventional two-dimensional electrolytic cell, and make filling
Particle surface electrification, becomes third pole, electrochemical reaction is enable to be strengthened on the surface of these granule electrode materials filled
Catalysis oxidation, thus considerably increase electrode surface area and shorten mass transfer distance, the organic contamination in final efficient degradation waste water
Object.Waste water can convert macromolecular to small organic molecule (alkane of carbochain≤6) when through three-dimensional electrocatalysis device, and
Part small molecule is decomposed, two-dimentional electrocatalysis device is entered back into, the Strong oxdiative of small organic molecule and ammonia nitrogen is realized, realizes waste water
Processing.
Further preferably are as follows: the catalyst filled in the three-dimensional electrocatalysis device is granule electrode, and the catalyst is
One of particle column-shaped active carbon, haydite, iron carbon ball, ferrite, plating transition glassy metal ball, vitreous carbon are a variety of.
By adopting the above technical scheme, the surface area of granule electrode is big, and the spacing between particle is small, it is possible to increase mass transfer speed
Degree improves current efficiency, to realize better electrocatalytic oxidation.
Further preferably are as follows: the three-dimensional electrocatalysis device bottom is provided with aerating system, the three-dimensional electrocatalysis device
The volume ratio of aeration quantity and waste water C are (1-15) in unit volume: 1.
By adopting the above technical scheme, it when waste water carries out electrocatalytic oxidation in three-dimensional electrocatalysis device, is passed through in device
Catalyst in device is disturbed, prevents from being mutually bonded between catalyst, while improving connecing between catalyst and waste water by air
Contacting surface product, fortifying catalytic oxidation, improves the catalysis oxidation efficiency.
Further preferably are as follows: the three-dimensional electrocatalysis device includes first anode plate and the first cathode plate, two-dimentional electro-catalysis
Device includes second plate plate, the second cathode plate, electrode plate, is titanium, first anode plate in the first cathode plate and the second cathode plate
With second plate plate be surface layer plate ruthenium iridium coating layer perhaps the titanium ruthenium iridium coating layer of iridium tantalum coating or iridium tantalum coating with a thickness of 5-
100μm；Spacing between first cathode plate and first anode plate is 200-500mm.
By adopting the above technical scheme, it is obtained through experiment, the spacing between first anode plate and the first cathode plate is 200-
When 500mm, electrocatalytic oxidation effect is best, while anode selects peptide as substrate, and cooperates ruthenium iridium coating layer or iridium tantalum coating
When, electro-catalysis effect is best.
Further preferably are as follows: the three-dimensional electrocatalysis device uses high-frequency direct-current power supply, and electrocatalysis oxidation reaction electric current is close
Degree is 25-30mA/cm2。
By adopting the above technical scheme, during three-dimensional electro-catalysis, electric current plays critically important effect to the decomposition of organic matter,
Electrocatalysis oxidation reaction current density is 25-30mA/cm2When, electrocatalytic oxidation effect is best.
Further preferably are as follows: in the two dimension electrocatalysis device, the connection type of electrode and power supply is bipolar system, and electric current is close
Degree is 5-50mA/cm2, the spacing between adjacent electrode plates is 3mm-5mm.
By adopting the above technical scheme, current density is controlled in 5-50mA/cm2, while the spacing between adjacent electrode plates
Effect for 3mm-5mm, two-dimentional electro-catalysis is best.Bipolar system electrolytic cell, the second plate plate and the second cathode plate at both ends are single
Electrode is connected with power supply, and intermediate electrode plate is all induction bipolar electrode, i.e. the one side of pole plate is anode, and another side is cathode.Electricity
Electric field can be generated between pole plate, generates isoelectric point, voltage is provided, and enhance electrocatalytic oxidation effect.
In conclusion the invention has the following advantages:
1, by first separating organic matter glar under acidic conditions, then iron cement is precipitated in neutral conditions, is kept away
Exempt from organic matter glar to ensure that organic matter glar can be separated in alkaline sedimentation together with iron cement.
2, by using the alkali tune agent of solution state, influence of the heat of solution to waste water is on the one hand prevented, is on the other hand realized
Pumping and metering, are more convenient the operation of automation.
3, by the way that three-dimensional electrocatalysis oxidation apparatus and two-dimentional electrocatalysis device is used in conjunction, remaining organic matter macromolecular is decomposed into
Fluorescence probe, then the Strong oxdiative of fluorescence probe and ammonia nitrogen is carried out, greatly improve the degree of purification to waste water.
4, it by using aerator, prevents from being mutually bonded between catalyst, while improving between catalyst and waste water
Contact area, fortifying catalytic oxidation, improves the catalysis oxidation efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of two-dimentional electrocatalysis device in embodiment 1-4；
Fig. 2 is the structural schematic diagram of part-structure in Fig. 1；
Fig. 3 is the structural schematic diagram of electrode assembly；
Fig. 4 is the structural schematic diagram of electric catalyticing system in embodiment 5-7；
Fig. 5 is the structural schematic diagram of three-dimensional electrocatalysis device part-structure.
Appended drawing reference: 1, three-dimensional electrocatalysis device；11, first anode plate；12, the first cathode plate；13, placed cavity；14,
One water inlet；15, the first water outlet；2, first shell；21, the first cabinet；211, downtake pipe；22, the first lid；23,
Fixed plate；24, loading plate；25, the first cavity；26, the second cavity；27, partition；3, aerator；4, two-dimentional electrocatalysis device；
41, the second water inlet；42, the second water outlet；5, second shell；51, the second cabinet；52, the second lid；53, subregion plate；54,
Zoneofoxidation；55, second exhaust pipe；6, electrode assembly；61, second plate plate；62, the second cathode plate；63, electrode plate；631,
One pole plate；632, the second pole plate；633, third pole plate；634, it is spaced pole plate；635, threaded rod；636, nut；64, block is pushed against；
641, card slot；65, side plate；7, guidance set；71, support plate；711, through-hole；72, plate is abutted.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
Embodiment 1: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, including following step
It is rapid: one: adjusting pH: raw wastewater being passed through into wastewater disposal basin using elevator pump, the raw wastewater of more batches of pharmacy can be in wastewater disposal basin
It saves bit by bit, and is stirred, be uniformly mixed more batches of raw wastewaters；The pH of raw wastewater is adjusted to 2 by hydrochloric acid, obtains waste water A.
Two: Fenton oxidation: waste water A is passed through into Fenton pond, measures rubbing for total COD amount in waste water A and ferrous ion
The mass parts ratio of that quality, hydrogen peroxide and COD are 1:0.05, and aqueous hydrogen peroxide solution dosage is calculated.When in waste water A
Ferrous ion molal weight and hydrogen peroxide molal weight ratio be greater than 0.1:1 when, aquae hydrogenii dioxidi is added into waste water A
Solution obtains waste water B, and generates organic matter glar.When the molal weight of ferrous ion and hydrogen peroxide in waste water A is than small
When 0.1:1, water-soluble ferrous salt and aqueous hydrogen peroxide solution are put into, obtains waste water B, and generate organic matter glar；Waste water B
The molal weight of ferrous ions and hydrogen peroxide ratio is 0.1:1.The precipitating generated in waste water B is passed through into filter press for waste water B
Supernatant is separated with organic matter glar.
Three: coagulating sedimentation: the supernatant of waste water B is passed through into coagulating sedimentation battery, by alkali tune agent by waste water B supernatant
The pH of liquid is adjusted to 7.5, and flocculant is added, obtains flocculation sedimentation and waste water C；
Four: electrocatalytic oxidation: waste water C being passed through to electrocatalytic oxidation system, is purified water after water outlet；Electrocatalytic oxidation system
For two-dimentional electrocatalysis device, hydraulic detention time 120min, the spacing in two-dimentional electrocatalysis device between electrode plate is 3mm, electricity
Current density is 5mA/cm2。
A kind of two dimension electrocatalysis device, as depicted in figs. 1 and 2, two-dimentional electrocatalysis device 4 includes second shell 5, is set to
Electrode assembly 6 in second shell 5, the guidance set 7 for contacting waste water with electrode assembly 6.Second shell 5 include it is hollow and on
End perforation and in the second cabinet 51 of cuboid, the second lid 52 (referring to Fig. 1) for being fixed on 51 upper surface of the second cabinet, perpendicular
Two blocks of subregion plates 53 in the second cabinet 51 are directly fixed on, are communicated with second exhaust pipe 55 (referring to Fig. 1) on the second cabinet 51, the
The second water inlet 41 and the second water outlet 42 are communicated on two cabinets 51.Subregion plate 53 divides the second cabinet 51 only to be pushed up for three
The zoneofoxidation 54 of portion's connection, successively snakelike connection between adjacent zoneofoxidation 54.
An electrode assembly 6 is provided in each zoneofoxidation 54.As shown in figure 3, electrode assembly 6 includes vertical and interval is set
The second plate plate 61 and the second cathode plate 62 set, two blocks of side plates being set between second plate plate 61 and the second cathode plate 62
65, the electrode plate 63 between two blocks of side plates 65, the abutting block 64 for fixed plate electrode 63 are set to.Side plate 65 is connected to second
The outermost of anode plate 61 and the second cathode plate 62, second plate plate 61, the second cathode plate 62 and two blocks of side plates 65 are by electrode
Plate 63 surrounds.
Electrode plate 63 is arranged in parallel with side plate 65, and electrode plate 63 includes six piece first pole plate fixed with second plate plate 61
631, it and fixed six piece of second pole plate 632 of the second cathode plate 62, is set between adjacent first pole plate 631 and adjacent second
Third pole plate 633 between pole plate 632, the interval pole plate 634 being set between the first pole plate 631 and the second pole plate 632.
The distance between adjacent first pole plate 631 is equal, and the distance between adjacent second pole plate 632 is equal.First pole plate
631 and second pole plate 632 correspond, and be located along the same line, interval pole plate 634 coincides with the first pole plate 631 and second
The interval of two block gaps setting is provided on the line of pole plate 632, and between each group of the first pole plate 631 and the second pole plate 632
Pole plate 634, therefore share 12 block gap pole plates 634.The first pole plate 631 and interval pole plate are covered in the middle part of third pole plate 633
634, the interval between adjacent spaces pole plate 634, the second pole plate 632 and interval pole plate 634, interval pole plate 634 are covered in phase
The interval of adjacent third pole plate 633.
Electrode plate 63 is fixedly connected by pushing against block 64, is pushed against and is offered card slot 641 on block 64.Third pole plate 633
End position, be provided with five pieces of abutting blocks 64, push against 64 end face of block and be connected to adjacent first pole plate 631 or adjacent
Between pole plate 634 or adjacent second pole plate 632,633 end of third pole plate is opened in card slot 641.In third pole plate 633
Portion position is provided with five pieces of abutting blocks 64, pushes against 64 end face of block and is connected to adjacent third pole plate 633,631 end of the first pole plate
In portion or interval 634 end of pole plate or the clamping of 632 end of the second pole plate and card slot 641.Adjacent the first pole plate 631, third
Spacing between pole plate 633 is all the same.
Level is equipped with same root threaded rod 635 between five abutting blocks 64 of same position, and 635 both ends of threaded rod are worn
To side plate 65, and it is threaded with nut 636, nut 636 is abutted with side plate 65.Second plate plate 61 and second plate plate
The connector connected to power supply there are two being respectively provided on 61.
As shown in Fig. 2, the electrode assembly 6 in each zoneofoxidation 54 is divided into three sections by guidance set 7 in the longitudinal direction, often
There are two guidance sets 7 for setting in a zoneofoxidation 54.Guidance set 7 include setting be fixed in zoneofoxidation 54 support plate 71,
The abutting plate 72 of setting is abutted with support plate 71, level offers the through-hole 711 that both ends penetrate through, through-hole 711 in support plate 71
Upside also penetrates through, and for installing electrode assembly 6, the side plate 65 of electrode assembly 6 is abutted with the vertical wall surface of through-hole 711；Support plate
71 upper surface flushes with 53 upper surface of subregion plate and is connected to 52 lower surface of the second lid.Abut 72 lower end surface of plate and side plate 65
Upper surface abuts, and abuts plate 72 and all cover through-hole 711 area of the through-hole 711 other than being used to install electrode assembly 6,
So that waste water can only pass through from electrode plate 63.It abuts and is bolted between plate 72 and support plate 71.
The water hole that aperture is less than 2mm is provided on partition 27 and loading plate 24.
In the present embodiment, aqueous hydrogen peroxide solution use mass concentration for 10% aqueous hydrogen peroxide solution；Alkali tune agent is adopted
With the sodium hydroxide solution of 5-30%；Flocculant uses bodied ferric sulfate；Second cathode plate is titanium plate, and second plate plate is 5 μ of plating
The titanium plate of m ruthenium iridium coating layer, electrode plate are titanium plate；The distance between electrode plate to the first pole plate and third pole plate, the second pole plate and
Spacing between third pole plate, interval pole plate and third pole plate.
Embodiment 2: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 1
Difference is, in a step, the pH of raw wastewater is adjusted to 4.5.
In two steps, use mass concentration for 22% aqueous hydrogen peroxide solution；The mass parts ratio of hydrogen peroxide and COD
For 1:0.2.In addition, investment is water-soluble when the molal weight ratio of the ferrous ion and hydrogen peroxide in waste water A is less than 0.1:1
Ferrous salt and aqueous hydrogen peroxide solution, obtain waste water B, and the molal weight ratio of waste water B ferrous ions and hydrogen peroxide is 0.5:
1。
In three steps, the pH of waste water B supernatant is adjusted to 8 by alkali tune agent, alkali tune agent uses the sodium carbonate of 5-25%
Solution.
In four steps, second plate plate is the titanium plate for plating 50 μm of ruthenium iridium coating layers；In two-dimentional electrocatalysis device between electrode plate
Spacing be 4mm, current density 20mA/cm2。
Embodiment 3: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 1
Difference is, in a step, the pH of raw wastewater is adjusted to 6.
In two steps, use mass concentration for 30% aqueous hydrogen peroxide solution；The mass parts ratio of hydrogen peroxide and COD
For 1:0.5.In addition, investment is water-soluble when the molal weight ratio of the ferrous ion and hydrogen peroxide in waste water A is less than 0.1:1
Ferrous salt and aqueous hydrogen peroxide solution, obtain waste water B, and the molal weight ratio of waste water B ferrous ions and hydrogen peroxide is 1:1.
In three steps, the pH of waste water B supernatant is adjusted to 9 by alkali tune agent, alkali tune agent uses the bicarbonate of 5-25%
Sodium solution.
In four steps, second plate plate is the titanium plate for plating 100 μm of ruthenium iridium coating layers；Spacing between electrode plate is 5mm, electric current
Density is 50mA/cm2。
Embodiment 4: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 3
Difference is, in two steps, pH is controlled between 2.5-4 by whole process by hydrochloric acid.
In three steps, alkali tune agent is using the sodium hydroxide solution of 5-30% and the mixed solution of 5-25% sodium carbonate liquor.
In four steps, the spacing between electrode plate is 5mm.
Embodiment 5: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 4
Difference is, in three steps, alkali tune agent is the mixed solution of 5-25% sodium carbonate liquor and 5-25% sodium bicarbonate solution.
In four steps, electrocatalytic oxidation system is successively being used in conjunction for three-dimensional electrocatalysis device and two-dimentional electrocatalysis device；Two
Tieing up the spacing in electrocatalysis device between electrode plate is 4mm, the body of aeration quantity and waste water C in three-dimensional electrocatalysis device unit volume
Product ratio is 15:1, hydraulic detention time 60min, and the catalyst in three-dimensional electrocatalysis device uses partial size for the plating transition of 3-10mm
Glassy metal ball.
First cathode plate and the second cathode plate use titanium plate, first anode plate and second plate plate to plate 5 μm of iridium using surface
The titanium plate of tantalum coating, the spacing between the first cathode plate and second plate plate are 200mm.Two-dimentional electrocatalysis device bottom is equipped with
Aerator, the volume ratio of aeration quantity and waste water C are 1:1 in three-dimensional electrocatalysis device unit volume.
A kind of electrocatalytic oxidation system, as shown in figure 4, including in interconnected three-dimensional electrocatalysis device 1 and embodiment 1
Two-dimentional electrocatalysis device 4.
As shown in figure 5, three-dimensional electrocatalysis device 1 includes first shell 2, first be vertically arranged in first shell 2 sun
Pole plate 11 and the first cathode plate 12, the first water inlet 14 and the first water outlet 15 (referring to fig. 4) being connected in first shell 2.
First shell 2 includes the perforation of hollow and upper end and is in the first cabinet 21 of cuboid, is fixed on 21 upper surface of the first cabinet
First lid 22, the two fixed plates 23 being fixed in the first cabinet 21.Downtake pipe 211 is communicated on first cabinet 21.
In two fixed plates 23, on one of vertical wall surface for being fixed on the first cabinet 21, another piece of fixed plate 23 is solid
Due between 21 two pieces of the first cabinet vertical wall surfaces, upper end is abutted with 22 lower surface of the first lid, and lower end and the first cabinet 21
The setting of bottom surface interval.The first cavity 25 and the second cavity 26 that fixed plate 23 divides the first cabinet 21 for bottom connection, two pieces solid
The loading plate 24 for carrying catalyst is horizontally fixed between fixed board 23, it is upper and lower two that the second cavity 26 is divided to by loading plate 24
Part, the space of 24 top of loading plate are the placed cavity 13 for placing catalyst, offer water hole on loading plate 24.Carrying
Be vertically fixed two pieces of partitions 27 on plate 24, first anode plate 11 and the first cathode plate 12 be set to partition 27 and fixed plate 23 it
Between.
First water inlet 14 is connected to 25 top half of the first cavity, and it is separate that the first water outlet 15 is connected to the first cabinet 21
On the vertical wall surface of first cavity, 25 side.It is provided with aerator 3 in second cavity 26 of 24 lower section of loading plate, to catalyst
It is aerated, catalyst is disturbed, improve the contact area between catalyst and waste water, improve electrocatalytic oxidation efficiency；Aeration
The air inlet pipe of device 3 extends to outside the first cabinet 21.
First water outlet 15 of three-dimensional electrocatalysis device 1 is connected to the second water inlet 41 of two-dimentional electrocatalysis device 4.
Embodiment 6: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 5
Difference is, in three steps, alkali tune agent is the hydroxide of 5-25% sodium carbonate liquor, 5-25% sodium bicarbonate solution and 5-30%
The mixed solution of sodium solution.
In four steps, the spacing between electrode plate is 5mm.Aeration quantity and waste water C in three-dimensional electrocatalysis device unit volume
Volume ratio be 10:1, the catalyst in three-dimensional electrocatalysis device uses partial size for the iron carbon ball of 3-10mm, vitreous carbon, ferrite
Mixture.First anode plate and second plate plate plate the titanium plate of 50 μm of iridium tantalum coatings, first anode plate and first using surface
Spacing between cathode plate is 400mm.
Embodiment 7: a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, with embodiment 6
Difference is, in four steps, the spacing between electrode plate is 3mm.
The volume ratio of aeration quantity and waste water C are 8:1 in three-dimensional electrocatalysis device unit volume, in three-dimensional electrocatalysis device
Catalyst using partial size or maximum width is the particle column-shaped active carbon of 3-10mm, haydite, iron carbon ball, ferrite, plated
Cross the mixture of glassy metal ball, vitreous carbon.First anode plate and second plate plate, which are used, plates 100 μm of iridium tantalum coatings using surface
Titanium plate, spacing between first anode plate and the first cathode plate is 500mm.
Comparative example 1: N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing is carried out using conventional Fenton oxidation
Method, comprising the following steps:
(1) initial stage pH is adjusted: raw wastewater is passed through into wastewater disposal basin, the raw wastewater of more batches of pharmacy can be saved bit by bit in wastewater disposal basin,
And stirred, it is uniformly mixed more batches of raw wastewaters；The pH of raw wastewater is adjusted to 5 by hydrochloric acid, obtains waste water X.
(2) Fenton oxidation: waste water X is passed through into Fenton pond, measures rubbing for total COD amount in waste water X and ferrous ion
The mass parts ratio of that quality, hydrogen peroxide and COD are 1:0.05, and aqueous hydrogen peroxide solution dosage is calculated.When in waste water X
Ferrous ion molal weight and hydrogen peroxide molal weight ratio be greater than 0.1:1 when, add aquae hydrogenii dioxidi into waste water X
Solution obtains waste water Y, and generates organic matter glar.When the molal weight of ferrous ion and hydrogen peroxide in waste water X is than small
When 0.1:1, water-soluble ferrous salt and aqueous hydrogen peroxide solution are put into, obtains waste water Y, and generate organic matter glar；Waste water B
The molal weight of ferrous ions and hydrogen peroxide ratio is 0.1:1.
(3) mid-term pH is adjusted, and the pH of waste water Y is adjusted to 8 by 5-30% sodium hydroxide solution, organic matter glar
Swelling generates the iron cement of ferrous hydroxide and iron hydroxide.
(4) be separated by solid-liquid separation: the hydrophily of organic matter glar is very high, and the aubergine of soy sauce is presented in entire waste water Y, can not
It is normally carried out the separation of organic matter glar.
Comparative example 2:N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, the difference with embodiment 5
It is, the spacing between first anode plate and the first cathode plate is 1000mm.
Comparative example 3:N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, the difference with embodiment 5
It is, the spacing between first anode plate and the first cathode plate is 800mm.
Comparative example 4:N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, the difference with embodiment 5
It is, the spacing in two-dimentional electrocatalysis device between electrode plate is 10mm.
Comparative example 5:N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, the difference with embodiment 5
It is, the spacing in two-dimentional electrocatalysis device between electrode plate is 20mm.
Characterization experiment:
1, wastewater treatment method evaluation experimental experimental subjects: embodiment 1-7 and comparative example 1, altogether 8 groups of laboratory samples.
Experimental method: N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater of Hangzhou pharmaceutical factory, it is useless by more batches
Water is mixed, and is bisected into 8 parts of waste water, respectively corresponds cooperation embodiment 1-7 and comparative example 1 carries out wastewater treatment.
Experimental result: the phenomenon that each step occurs in wastewater treatment process, is recorded and (does not change, is not required to
Record), wastewater treatment method evaluation experimental result record is as shown in table 1.The COD of embodiment 1-8 final outflow water, ammonia nitrogen is dense
Degree, SS, coloration are detected and are recorded, and each index record of final outflow water is as shown in table 2.
1 wastewater treatment method evaluation experimental result record sheet of table
Each index result record sheet of 2 final outflow water of table
Data analysis: from Tables 1 and 2 it is found that waste water can be handled by implementing sample 1-8, and it is dirty to meet local garden
Water discharge standard (COD≤350mg/L, ammonia nitrogen≤35mg/L), and the grade III Standard in " integrated wastewater discharge standard "
(GB8978-1996): COD≤1000mg/L, SS≤400mg/L, coloration≤80, ammonia nitrogen≤50mg/L.And in comparative example waste water
Glar be attached together with water, can not be normally separated by solid-liquid separation, i.e., conventional Fenton's reaction is at waste water
Reason.
In the conventional Fenton oxidation operation of comparative example 1, due to the parent of Organic substance in water glar under alkaline condition that gives up
It is aqueous, iron cement and organic matter glar can not be cleared out together, so that waste water becomes the mixture of solid-liquid, and with conventional mistake
Filter or filters pressing operation can not clear out organic matter glar, can not handle waste water.And in the treatment process of embodiment,
Organic matter glar is discharged in acid condition again, then is tuned into alkalinity and iron cement is discharged, guarantees the normal processing of waste water.
2, influence experimental subjects of the three-dimensional and two-dimentional electrocatalysis device to scavenging effect: embodiment 5-7, comparative example 2-5,
7 groups of laboratory samples altogether.
Experimental method: N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater of Hangzhou pharmaceutical factory, it is useless by more batches
Water is mixed, and is bisected into 5 parts of waste water, is respectively corresponded cooperation embodiment 5-7 and comparative example 2-5 and is carried out wastewater treatment, detection
And record in embodiment 5-7, comparative example 2-5, waste water enters the COD concentration of (test point is 1.), ammonia before three-dimensional electrocatalysis device
Nitrogen concentration, waste water is from the COD concentration of (test point is 2.), ammonia nitrogen concentration after the water outlet of three-dimensional electrocatalysis device；Waste water is urged from two-dimentional electricity
The COD concentration of (test point is 3.), ammonia nitrogen concentration after water outlet are set in makeup, and are calculated after waste water passes through three-dimensional electrocatalysis device, three-dimensional
Electrocatalysis device is to the removal rate of COD and ammonia nitrogen, and after two-dimentional electrocatalysis device, two-dimentional electrocatalysis device is to COD and ammonia nitrogen
Removal rate.
Test point 1. it is corresponding be COD and ammonia nitrogen in electric catalyticing system removal rate, it is three-dimensional electricity that test point is 2. corresponding
The removal rate of catalytic unit COD and ammonia nitrogen, test point 3. it is corresponding be two-dimentional electrocatalysis device COD and ammonia nitrogen removal rate.
Experimental result: three-dimensional and two-dimentional electrocatalysis device records the experimental result that scavenging effect influences as shown in table 3.
The three-dimensional and two-dimentional electrocatalysis device of table 3 influences result record sheet to scavenging effect
Data analysis: in embodiment 5-7, the removal rate of two-dimentional electrocatalysis device COD can achieve 60% or so, ammonia nitrogen
Removal rate can achieve between 25-30%, and the removal rate of three-dimensional electrocatalysis device COD can achieve 55% or so, ammonia nitrogen removal
Rate can achieve 95% or so, and can meet local garden sewage drainage standard (COD≤350mg/L, ammonia nitrogen≤35mg/L), with
And the grade III Standard (GB8978-1996) in " integrated wastewater discharge standard ".Illustrate the first anode in three-dimensional electrocatalysis device
Plate and the preferred 200-500mm distance of the first cathode plate have extraordinary electro-catalysis effect, the electrode in two-dimentional electrocatalysis device
The preferred 3-5mm distance of plate spacing has extraordinary electro-catalysis effect.
In comparative example 2-3, since the distance of first anode plate and the first cathode plate in three-dimensional electrocatalysis device is too big (right
Ratio 2 is 1000mm, and comparative example 3 is 800mm) so that electrocatalytic oxidation effect is not the three-dimensional electricity embodied in data very well
The COD removal rate of catalytic unit is less than 20%, while ammonia nitrogen removal frank does not have substantially, while having also affected two-dimentional electro-catalysis dress
The removal rate set；Since the main function of three-dimensional electrocatalysis device is that larger molecular organics are decomposed into small organic molecule, two
The effect of two-dimentional electrocatalysis device is that small molecule is carried out Strong oxdiative decomposition, so when the COD removal rate of three-dimensional electrocatalysis device
After reduction, larger molecular organics enter in two-dimentional electrocatalysis device, and are not belonging to the treated substance that two-dimentional electrocatalysis device is good at,
Result in the decline of two-dimentional electrocatalysis device COD and ammonia nitrogen removal frank.
In comparative example 4-5, since the electrode plate distance of two-dimentional electrocatalysis device is too big, (comparative example 4 is 10, and comparative example 5 is
20mm), so that the effect of electro-catalysis is not that very well, the COD removal rate of the two-dimentional electrocatalysis device in data at embodiment is insufficient
5%, ammonia nitrogen removal frank only has 10% or so even lower.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (10)
1. a kind of N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method, which is characterized in that including following step
It is rapid:
One: adjusting pH: the pH of raw wastewater being adjusted to 2-6, obtains waste water A；
Two: the mixture or aquae hydrogenii dioxidi of water-soluble ferrous salt and aqueous hydrogen peroxide solution Fenton oxidation: are added into waste water A
Solution obtains waste water B, is separated by solid-liquid separation, and obtains waste water B supernatant；
Three: coagulating sedimentation: the pH of waste water B being adjusted to 7.5-9, flocculant is added, obtains flocculation sedimentation and waste water C；
Four: electrocatalytic oxidation: waste water C being passed through to electrocatalytic oxidation system, is purified water after water outlet；
The electrocatalytic oxidation system is two-dimentional electrocatalysis device (4)；
The mass concentration of hydrogen peroxide is 10%-30% in the aqueous hydrogen peroxide solution.
2. N- p-benzoyl according to claim 1-Pidolidone pharmaceutical intermediate wastewater processing method, feature
Be, in two step, the mass parts ratio of hydrogen peroxide and COD is 1:(0.05-0.5), when waste water A ferrous ions with
When the molal weight ratio of hydrogen peroxide is greater than 0.1:1, aqueous hydrogen peroxide solution is added into waste water A；When waste water A ferrous ions
When being less than 0.1:1 with the molal weight ratio of hydrogen peroxide, aqueous hydrogen peroxide solution and water-soluble ferrous salt are added into waste water A,
The molal weight ratio of waste water B ferrous ions molal weight and hydrogen peroxide is (0.1-1): 1.
3. N- p-benzoyl according to claim 2-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, during two step, pH is controlled between 2.5 ~ 4.
4. N- p-benzoyl according to claim 1-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, in three step, pH is adjusted to by 7.5-9 by alkali tune agent, the alkali tune agent is the hydrogen-oxygen that mass fraction is 5-30%
Change sodium solution, mass fraction is 5-25 % sodium carbonate liquor, mass fraction is one of 5-25% sodium bicarbonate solution or more
Kind.
5. N- p-benzoyl according to claim 1-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, the electrocatalytic oxidation system is three-dimensional electrocatalysis device (1) and two-dimentional electrocatalysis device (4), and waste water C sequentially enters three
Tie up electrocatalysis device (1) and two-dimentional electrocatalysis device (4).
6. N- p-benzoyl according to claim 5-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, the catalyst filled in the three-dimensional electrocatalysis device (1) is granule electrode, and the catalyst is particle column activity
One of charcoal, haydite, iron carbon ball, ferrite, plating transition glassy metal ball, vitreous carbon are a variety of.
7. N- p-benzoyl according to claim 5-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, described three-dimensional electrocatalysis device (1) bottom is provided with aerating system, in described three-dimensional electrocatalysis device (1) unit volume
The volume ratio of aeration quantity and waste water C are (1-15): 1.
8. N- p-benzoyl according to claim 5-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, the three-dimensional electrocatalysis device (1) includes first anode plate (11) and the first cathode plate (12), two-dimentional electrocatalysis device
It (4) include second plate plate (61), the second cathode plate (62), electrode plate (63), the first cathode plate (12) and the second cathode plate
It (62) is titanium in, first anode plate (11) and second plate plate (61) are the titanium that ruthenium iridium coating layer or iridium tantalum coating are plated in surface layer, ruthenium
Iridium coating layer or iridium tantalum coating with a thickness of 5-100 μm；Spacing between first cathode plate (12) and first anode plate (11) is
200-500mm。
9. N- p-benzoyl according to claim 5-Pidolidone pharmaceutical intermediate wastewater processing method, feature
It is, the three-dimensional electrocatalysis device (1) uses high-frequency direct-current power supply, and electrocatalysis oxidation reaction current density is 5-50mA/
cm2。
10. N- p-benzoyl according to claim 5-Pidolidone pharmaceutical intermediate wastewater processing method, special
Sign is, in the two dimension electrocatalysis device (4), the connection type of electrode and power supply is bipolar system, current density 5-50mA/
cm2, the spacing between adjacent electrode plates (63) is 3mm-5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910632465.1A CN110330153A (en) | 2019-07-13 | 2019-07-13 | N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910632465.1A CN110330153A (en) | 2019-07-13 | 2019-07-13 | N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110330153A true CN110330153A (en) | 2019-10-15 |
Family
ID=68146742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910632465.1A Pending CN110330153A (en) | 2019-07-13 | 2019-07-13 | N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110330153A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239294A (en) * | 2020-09-25 | 2021-01-19 | 西南林业大学 | Method for treating pharmaceutical wastewater by micro-electrolysis chemical precipitation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035444A2 (en) * | 2003-10-10 | 2005-04-21 | Ohio University | Electro-catalysts for the oxidation of ammonia in alkaline media |
| CN101955280A (en) * | 2010-08-13 | 2011-01-26 | 南京赛佳环保实业有限公司 | Technology for processing high-concentration organic wastewater in composite electrochemical method |
| CN204702628U (en) * | 2015-05-27 | 2015-10-14 | 苏州澄江节能科技有限公司 | Water color ink liquid waste treatment system |
| CN106587445A (en) * | 2016-09-09 | 2017-04-26 | 沈阳工业大学 | Pretreatment method of antibiotic production waste water |
| CN108892212A (en) * | 2018-08-21 | 2018-11-27 | 沈阳华清节能环保科技有限公司 | A kind of electrocatalytic method sewage disposal system and its method |
-
2019
- 2019-07-13 CN CN201910632465.1A patent/CN110330153A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035444A2 (en) * | 2003-10-10 | 2005-04-21 | Ohio University | Electro-catalysts for the oxidation of ammonia in alkaline media |
| CN101955280A (en) * | 2010-08-13 | 2011-01-26 | 南京赛佳环保实业有限公司 | Technology for processing high-concentration organic wastewater in composite electrochemical method |
| CN204702628U (en) * | 2015-05-27 | 2015-10-14 | 苏州澄江节能科技有限公司 | Water color ink liquid waste treatment system |
| CN106587445A (en) * | 2016-09-09 | 2017-04-26 | 沈阳工业大学 | Pretreatment method of antibiotic production waste water |
| CN108892212A (en) * | 2018-08-21 | 2018-11-27 | 沈阳华清节能环保科技有限公司 | A kind of electrocatalytic method sewage disposal system and its method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239294A (en) * | 2020-09-25 | 2021-01-19 | 西南林业大学 | Method for treating pharmaceutical wastewater by micro-electrolysis chemical precipitation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106277591B (en) | Landfill leachate nanofiltration concentrate processing method | |
| CN104743717A (en) | Method and system for reduction of concentrated brine | |
| CN106830536A (en) | A kind of advanced treatment process of ferment antibiotics waste water | |
| CN105540947A (en) | Method and system for processing drilling wastewater | |
| Xu et al. | Sulfite assisted rotating disc electrocoagulation on cadmium removal: parameter optimization and response surface methodology | |
| CN107522267A (en) | A kind of multistage out-phase three-dimensional electrochemical reaction unit for waste water treatment | |
| CN103539234A (en) | Integrated processing method of fracturing flow-back fluid | |
| CN103936106A (en) | Electrochemical synchronous nitrogen and phosphorus removal apparatus and municipal sewage treatment method | |
| CN103936208A (en) | Efficient micro-electrolysis multiphase flow air flotation reactor | |
| CN110330153A (en) | N- p-benzoyl-Pidolidone pharmaceutical intermediate wastewater processing method | |
| CN101913689A (en) | Multifunctional high-efficiency sewage-treating reactor | |
| CN204022601U (en) | The micro-electrolysis advanced oxidation of MEO reactor | |
| CN105565610A (en) | Industrial wastewater deep treatment process | |
| CN210261454U (en) | Mariculture tail water treatment system | |
| CN105217846A (en) | Cold rolling alkaline waste discharge advanced treatment system and treatment process | |
| CN108358375A (en) | A kind of industrial sewage process method | |
| CN105060656A (en) | Biochemical system auxiliary device and application thereof | |
| CN201785231U (en) | Multifunctional high-efficiency sewage treatment reactor | |
| CN203754535U (en) | Efficient micro-electrolysis multiphase flow air flotation reactor | |
| CN102795695B (en) | Electrochemical oxidation method for removing biological-source organic nano-matters in biochemical wastewater treatment yielding water | |
| CN209906552U (en) | Wastewater treatment system containing ammonia nitrogen | |
| El-Shazly | Investigation for the possibility of nitrogen removal from industrial effluent of bone glue industry using a batch electrocoagulation unit with monopolar horizontal electrodes | |
| CN107640810A (en) | High pressure electric flocculation sewage disposal system | |
| CN205442965U (en) | Wastewater treatment device | |
| CN201908136U (en) | Electrode plate of EFT inertia composite electrode and electrolytic equipment comprising electrode plate |
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 | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20220701 |