CN218810653U - Contain processing apparatus of nitrate radical waste liquid - Google Patents
Contain processing apparatus of nitrate radical waste liquid Download PDFInfo
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- CN218810653U CN218810653U CN202121539776.2U CN202121539776U CN218810653U CN 218810653 U CN218810653 U CN 218810653U CN 202121539776 U CN202121539776 U CN 202121539776U CN 218810653 U CN218810653 U CN 218810653U
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- 239000007788 liquid Substances 0.000 title claims abstract description 128
- 239000002699 waste material Substances 0.000 title claims abstract description 89
- 238000012545 processing Methods 0.000 title claims abstract description 22
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 title abstract description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 198
- 239000007789 gas Substances 0.000 claims abstract description 109
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013589 supplement Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 19
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000005684 electric field Effects 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 84
- 238000005868 electrolysis reaction Methods 0.000 claims description 67
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 238000001514 detection method Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000004868 gas analysis Methods 0.000 claims description 16
- 238000012546 transfer Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- 230000033116 oxidation-reduction process Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 10
- 238000005341 cation exchange Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 74
- 239000000243 solution Substances 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 17
- 229910017604 nitric acid Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 12
- -1 nitrate ions Chemical class 0.000 description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 159000000014 iron salts Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 208000028571 Occupational disease Diseases 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The utility model discloses a processing device of waste liquid containing nitrate radical, which comprises an electrolytic reaction tank, an electrolytic separator, an electrolytic anode, an electrolytic cathode, an electrolytic power supply, a nitrogen oxide gas processing device and a supplement storage tank; the electrolytic separator divides the electrolytic reaction tank into an anode area and a cathode area; the top of the cathode area is provided with a first cover plate with an air outlet, and the air outlet of the first cover plate is connected with the nitrogen oxide gas treatment device; the supplement storage tank is used for containing supplements to be added to the anode region or the cathode region and is connected with the anode region or the cathode region; the electrolytic separator is a material capable of separating the electrolytic reaction cell and effectively preventing the anions in the catholyte from migrating to the anolyte under the action of an electric field, and comprises but is not limited to a cation exchange membrane and a bipolar membrane. The utility model discloses a processing apparatus contains the nitrate waste liquid through electricity collaborative chemical treatment, effectively decomposes the nitrate ion, makes it reach the effect that shows to reduce or get rid of.
Description
Technical Field
The utility model belongs to a processing apparatus of industrial waste liquid, concretely relates to processing apparatus who contains nitrate radical waste liquid.
Background
The nitrogen-containing waste liquid generated in industrial production is generally from nitric acid or a mixed raw material containing a nitrate component used in production, and the waste liquid contains nitric acid and/or nitrate. Nitrate-containing feedstocks are now commonly used in industrial chemical production: nitric acid type metal passivation solution, nitric acid type tin stripping water, nitric acid type electroplating wire de-clamping water, nitric acid-containing metal cleaning solution, nitrate-containing metal plating solution and the like. Nitric acid type metal passivation solutions use nitric acid as one of the main components, most commonly used for passivation of stainless steel. Nitric acid type tin stripping solution is the solution most commonly used in the industry for dissolving and removing the corrosion-resistant tin coating in the circuit board manufacturing process, and the main component of the nitric acid type tin stripping solution is nitric acid, and the nitric acid type tin stripping solution also contains ferric nitrate and/or other optional additives. The nitric acid type electroplating line de-clamping water is a solution for cleaning a clamp on an electroplating production line, mainly contains nitric acid, and may further contain nitrate to assist in increasing the dissolving speed of metal impurities plated on the clamp. The metal cleaning solution containing nitric acid is commonly used for cleaning stainless steel or titanium alloy products in the metal processing industry, and is a solution for removing an oxide layer and rust on the surface of a metal product so as to reproduce the color of metal on the surface of the metal product. The most common metal plating solutions containing nitrate ions are those containing nitrate as the main salt in the plating solution or electroless plating solution, for example, silver plating solutions often contain silver nitrate as the main salt of the plating solution, and the waste solution still contains a large amount of nitrate ions. In view of the toxicity of nitrate ions, users usually send waste liquid containing nitrate to qualified environmental protection companies for treatment, thereby resulting in higher costs.
However, nitrate ions are difficult to form coprecipitation or to be adsorbed due to high solubility and good stability of nitrate in water, and it is difficult to remove nitrate ions from waste liquid by using traditional simple water treatment technologies such as lime softening and filtering. Therefore, the technology and the device for treating the nitrate ions in the waste liquid still have high research value.
SUMMERY OF THE UTILITY MODEL
The utility model provides a processing apparatus who contains nitrate waste liquid adopts the device can effectively decompose the nitrate ion that contains in the nitrate waste liquid and make it reach the effect that shows to reduce or get rid of.
In order to solve the technical problem, the utility model discloses the technical scheme who takes is:
a treatment device for nitrate radical-containing waste liquid comprises an electrolytic reaction tank, an electrolytic separator, an electrolytic anode, an electrolytic cathode, an electrolytic power supply, a nitrogen oxide gas treatment device and a supplement storage tank; the electrolytic separator divides the electrolytic reaction tank into an anode region and a cathode region; the top of the cathode area is provided with a first cover plate with an air outlet, and the air outlet of the first cover plate is connected with the nitrogen oxide gas treatment device; the supplement storage tank is used for containing supplements to be added to the anode region or the cathode region and is connected with the anode region or the cathode region; the electrolytic separator is a material capable of separating the electrolytic reaction cell and effectively preventing the anions in the catholyte from migrating to the anolyte under the action of an electric field, and includes, but is not limited to, cation exchange membranes, bipolar membranes and the like.
The electrolytic anode is selected from one or two or more of graphite, bare metal, metal electrode with electrolytic coating or inert metal plated surface, and other conductive objects. The bare metal is any one of platinum, gold and an alloy containing platinum and/or gold; the metal material in the metal electrode with the surface coated with the electrolytic coating or plated with the inert metal is at least one of titanium, platinum, gold, silver, copper, iron, aluminum, an alloy containing one or two or more of the above metals, and stainless steel; the inert metals include, but are not limited to, platinum, gold; the other conductive objects are non-metal objects with surfaces coated with conductive coatings or surfaces plated with metals.
The electrolytic cathode is selected from one or two or more of graphite, bare metal, metal electrode plated with inert metal on the surface and other conductive objects. The bare metal is any one of platinum, gold, copper, iron and stainless steel or an alloy containing at least one of the metals, and when the catholyte does not contain sulfuric acid, the bare metal can also be any one of titanium and an alloy containing titanium; the metal material in the metal electrode plated with the inert metal is at least one of titanium, platinum, gold, silver, copper, iron, aluminum, an alloy containing one or two or more of the metals and stainless steel; the inert metal includes, but is not limited to, platinum, gold, and titanium when sulfuric acid is not present in the catholyte; and the surfaces of the other conductive objects are plated with non-metallic objects of inert metal. When the electrolytic cathode adopts an iron bare metal electrode, besides the electrochemical reduction reaction on the electrolytic cathode, a chemical reaction between the iron metal of the electrolytic cathode and the acidic catholyte can also occur, and the balance point of the two reactions can be adjusted by the electrolytic current. When the electrolysis current is small, the chemical reaction of the iron metal of the electrolysis cathode and the acidic catholyte occurs in the cathode area to generate new ferrous ions, and the iron ions can be supplemented in the catholyte in the electrolysis process.
Preferably, the electrolytic cathode is one or two or more of iron, platinum, gold, and an electrode with platinum and/or gold plated on the surface.
The nitrogen oxide gas treatment device is one or more of a commercial nitrogen oxide gas normal-temperature chemical reaction treatment device and a glowing metal high-temperature reduction nitrogen oxide gas treatment device consisting of a catalytic metal placing cavity and a heating device.
The nitrogen oxide gas treatment device adopts a multi-stage series connection mode, so that the gas discharged by the nitrogen oxide gas treatment device meets the requirement of environmental protection indexes.
The gas outlet of first apron with between the nitrogen oxide gas processing apparatus, or set up pump drainage device between the multistage nitrogen oxide gas processing apparatus who establishes ties for the tail gas pump drainage who comes from negative pole district or nitrogen oxide gas processing apparatus with higher speed, work as nitrogen oxide gas processing apparatus can also promote the reaction for nitrogen oxide gas normal atmospheric temperature chemical reaction processing apparatus time. The pumping device is an air pump or a vacuum ejector.
The electrolysis power supply is provided with a current regulator or is connected with the current regulator and used for regulating the current output by the electrolysis power supply according to the electrolysis condition or controlling the on or off of the electrolysis power supply. The current output by the electrolysis power supply can control the oxidation-reduction potential of the electrolyte in the cathode region; the oxidation-reduction potential of the electrolyte in the cathode region is rapidly reduced by improving the electrolytic current, so that the concentration of ferrous ions in the cathode electrolyte is increased, the reaction treatment of nitrate ions is accelerated, the power consumption is optimized, and the reaction treatment time of the nitrate ions can be shortened.
The electrolytic power supply adopts a pulse type electrolytic power supply, when colloid or sludge is generated in the electrolyte in the treatment process, an electrolytic partition is attached to block an ion channel, the electrolytic operation is stopped periodically and discontinuously by using the current output by the pulse type power supply, and the sludge attached to the electrolytic partition is dissolved and falls off from the electrolytic partition in the period of temporarily stopping the action of the electric field.
The anode region and/or the cathode region are/is provided with an electrolyte detection device; the electrolyte detection device comprises at least one detection device of a liquid level meter, a specific gravity meter, an acidimeter, an oxidation-reduction potentiometer, a photoelectric colorimeter, a thermometer and a pH meter, and is used for detecting corresponding process parameters in the electrolyte in the anode region and/or the electrolyte in the cathode region and performing process control management. When the electrolyte detection device comprising the oxidation-reduction potentiometer is arranged in the cathode area, the nitrate radical digestion condition can be calculated by monitoring the concentration content of ferrous ions in the catholyte through detecting the oxidation-reduction potential of the catholyte.
A stirring device is arranged in the anode region and/or the cathode region, so that different components of the electrolyte in each subarea are uniformly distributed; the stirring device is a circulating liquid flow stirring device, or an impeller stirring device, or the combination of the circulating liquid flow stirring device and the impeller stirring device. The circulating liquid flow stirring device comprises a liquid outlet pipe, a return pipe, a controlled pump and/or a valve.
The treatment device comprises a tail gas treatment device used for treating the tail gas separated out in the electrolysis anode area. And a second cover plate with an air outlet is arranged at the top of the anode area, and the air outlet of the second cover plate is connected with the air inlet of the tail gas treatment device. When more than one exhaust gas treatment device is used, the exhaust gas treatment devices are connected in series.
The treatment device comprises a cathode electrolyte preparation tank for preparing and temporarily storing the cathode electrolyte to be subjected to electrolytic treatment; the catholyte preparation tank is connected with the cathode region.
The treatment device comprises a waste liquid pretreatment tank for pretreating waste liquid; the waste liquid pretreatment tank is connected with the cathode electrolyte preparation tank or the cathode area.
The treatment device comprises a solid-liquid separator for carrying out solid-liquid separation on the treatment liquid with solid precipitates or the treatment liquid with solids separated out in the treatment process; the solid-liquid separator is arranged between any two similar or dissimilar tanks in the catholyte preparation tank, the waste liquid pretreatment tank and the cathode region, or is connected with one of the cathode region and the anode region to form a loop.
The treatment device comprises a water-oil separator, and the water-oil separator is used for carrying out water-oil separation pretreatment on the waste liquid containing nitrate radicals or the pretreated waste liquid and is arranged between any two similar or dissimilar tanks in the cathode electrolyte preparation tank, the waste liquid pretreatment tank and the cathode area.
The treatment device comprises a transfer tank for storing a solution to be treated or in the treatment process; the transfer tank is arranged between any two of the same type or different types of the catholyte preparation tank, the waste liquor pretreatment tank, the cathode region, the solid-liquid separator and the water-oil separator, or is connected with one of the catholyte preparation tank, the waste liquor pretreatment tank, the cathode region and the anode region. When a plurality of transit tanks are adopted at the same position, the transit tanks can be arranged in parallel or in series.
The replenisher storage tank is connected with one of an anode region, a cathode region, a catholyte preparation tank, a waste liquid pretreatment tank and a transit tank connected with the anode region or the cathode region through a feeding pump or solid feeding equipment.
The treatment device comprises a cold-heat temperature exchanger which is arranged in one of the anode region, the cathode region and a transit tank connected with the anode region or the cathode region and used for adjusting the temperature of the electrolyte in the anode region or the cathode region.
The processing device comprises a nitrogen oxide gas analysis detector, performs data detection on the content of gas separated out from the cathode region, and controls the production process according to the detection result; the nitrogen oxide gas analysis detector is arranged at the gas outlet of the cathode area or the gas outlet of the nitrogen oxide gas treatment device.
The processing device comprises an automatic feeding controller, the signal output end of the automatic feeding controller is connected with the signal input end of at least one of a feeding pump, a solid feeding device, a pumping and discharging device, a tail gas processing device, a current regulator and a cold-heat temperature exchanger, and the automatic feeding controller controls the operation of the device connected with the signal output end of the automatic feeding controller according to a time program and/or the detection result of an electrolyte detection device and/or a nitrogen oxide gas analysis detector.
Preferably, the signal input end of the automatic feeding controller is connected with the signal output end of at least one of the electrolyte detection device and the nitrogen oxide gas analysis detector.
Preferably, the treatment device comprises a COD detector for monitoring COD of the liquid passing through the water-oil separator so as to remind of replacing parts of the water-oil separator or maintaining the water-oil separator in time; the COD detector is arranged in a flow pipeline of liquid obtained after the treatment of the water-oil separator.
The utility model has the advantages that:
the utility model discloses a processing apparatus contains the nitrate waste liquid through electricity collaborative chemical treatment, effectively decomposes the nitrate ion, makes it reach the effect that shows to reduce or get rid of.
Adopt the utility model discloses the device is handled and is contained the nitrate waste liquid, and easy operation safe and reliable degree of automation is high, can reduce workman's intensity of labour and occupational disease.
The utility model discloses a contain nitrate waste liquid treatment device simple structure cost is low, and the fund input is few, and it is few to occupy the place, and the waste liquid treatment capacity is big, and the environment improves obviously.
Drawings
FIG. 1 is a schematic view of an apparatus for treating a nitrate nitrogen-containing waste liquid according to example 1;
FIG. 2 is a schematic view of an apparatus for treating a nitrate nitrogen-containing waste liquid in example 2;
FIG. 3 is a schematic view of an apparatus for treating a nitrate nitrogen-containing waste liquid according to examples 3 and 4;
FIG. 4 is a schematic view of an apparatus for treating a nitrate nitrogen-containing waste liquid of example 5;
FIG. 5 is a schematic view of nitrate nitrogen-containing waste liquid treatment apparatuses according to examples 6 and 7.
Reference numerals: 1-an anode region; 2-a cathode region; 3-an electrolytic separator; 4-an electrolytic anode; 5-an electrolytic cathode; 6-an electrolytic power supply; 7-a first nitrogen oxide gas treatment device; 8-a second oxynitride gas treatment unit; 9-a first cover plate; 10-a second cover plate; 11-a first air outlet; 12-a second outlet; 13-a first feed opening; 14-a second feed opening; 15-a first impeller agitator; 16-a second impeller mixer; 17-a recycle stream agitator; 18-a first vacuum ejector; 19-a second vacuum ejector; 20-a third vacuum ejector; 21-a tail gas treatment device; 22-a water-oil separator; 23-a first solid-liquid separator; 24-a catholyte preparation tank; 25-a first transit trough; 26-a second transfer tank; 27-a first supplement reservoir; 28-a second replenisher reservoir; 29-automatic feeding controller; 30-a cold-hot temperature exchanger; 31-a first nitrogen oxide gas analyzer detector; 32-second nitrous oxide gas analysis detector; 33-a waste liquid pretreatment tank; 34-a third nitrogen oxide gas treatment device; 35-first electrolyte detection means; 36-a second electrolyte detection device; 37-a third feed inlet; 38-a third supplement reservoir; 39-a third transit trough; 40-a fourth transit trough; 41- -fifth transfer tank; 42-a sixth transit trough; 43-a seventh transit trough; 44-first solids dosing equipment; 45-a second solid-liquid separator; 46-a third solid-liquid separator; 47-second solids addition equipment; 48-COD detector; 49-fourth supplement reservoir.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the nitrate nitrogen-containing waste liquid treatment apparatus of example 1 includes an electrolytic separator 3, an electrolytic reaction tank partitioned into an anode region 1 and a cathode region 2 by the electrolytic separator 3, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, a first nitrogen oxide gas treatment apparatus 7, a catholyte preparation tank 24, a first transfer tank 25, a second transfer tank 26, a first replenisher storage tank 27, a water-oil separator 22, and a first solid-liquid separator 23. The electrolytic separator 3 is a cationic membrane; the electrolysis power supply 6 is a pulse electrolysis power supply; the first nitrogen oxide gas treatment device 7 is a nitrogen oxide high-temperature reduction treatment device. The electrolysis anode 4 is positioned in the anode region 1 and is connected with the anode of the electrolysis power supply 6, and the electrolysis cathode 5 is positioned in the cathode region 2 and is connected with the cathode of the electrolysis power supply 6. The top of the cathode area 2 is provided with a first cover plate 9, and the first cover plate 9 is provided with a first air outlet 11, a first feeding port 13 and a second feeding port 14. The first nitrogen oxide gas treatment device 7 is connected with the cathode region 2 through a first gas outlet 11; a first nitrogen oxide gas analyzer 31 is provided at the gas outlet of the first nitrogen oxide gas treatment device 7. The cathode region 2 is provided with a circulating liquid flow agitator 17.
The waste liquid to be treated containing nitrate and ferric salt in the cathode electrolyte preparation tank 24 is separated into oil phase by the water-oil separator 22, the solution enters the first transfer tank 25, then is separated into solid impurities by the first solid-liquid separator 23, flows into the second transfer tank 26, and finally is fed into the cathode region 2 through the second feeding port 14. The first extender storage tank 27 is loaded with the acid catholyte extender and fed to the cathode section 2 through the first feed port 13.
The device is used for treating the waste liquid containing nitrate radicals, and comprises the following specific steps:
the method comprises the following steps: preparing electrolyte according to the component proportion of the electrolyte in the anode region and the cathode region shown in the table-1, and adding the electrolyte into the anode region and the cathode region respectively;
step two: immersing an electrolytic anode into the electrolyte in the anode region and connecting the electrolytic anode with the anode of an electrolytic power supply, and immersing an electrolytic cathode into the electrolyte in the cathode region and connecting the electrolytic cathode with the cathode of the electrolytic power supply;
step three: starting an electrolysis power supply to start the electrolyte to perform electrochemical reaction, and decomposing nitrate radical-containing liquid in an electrolysis cathode region;
step four: and (3) finishing the electrolysis operation, wherein the operation time is 35 hours, sampling and detecting the electrolyte in the electrolysis cathode region of the electrolysis reaction tank, and recording the detection result in table-1.
In the electrolysis process, waste liquid to be treated containing nitrate radicals and iron salts is pretreated and then fed into a cathode area, the concentration and the pH value of iron ions in the catholyte are controlled according to a table-1, and sulfuric acid serving as an acid catholyte supplement is fed into the cathode area to keep the pH value constant, so that iron hydroxide in the catholyte is prevented from being separated out. Oxygen is separated out from the anode area in the electrolytic process, nitrate radicals are generated in the cathode area to react and produce nitric oxide gas. And treating the nitric oxide gas by a nitrogen oxide high-temperature reduction treatment device to generate nitrogen and discharging the nitrogen. In the process, the treatment effect can be known through data displayed by the nitrogen oxide gas analysis detector.
In example 1, the anolyte is an alkaline solution and the catholyte is an acidic solution, so that the hydroxide adhered with iron and precipitated on the electrolytic separation membrane is dissolved and falls off during the period of stopping the operation current by adopting the pulse type electrolytic power supply, thereby avoiding influencing the electrolytic operation.
The treatment of the waste liquid containing nitrate radical adopts a process method of treating the waste liquid one by one in each tank, and only the acid extender is added into a cathode area without adding the waste liquid in the midway, so that the nitrate radical in the waste liquid can reach the index of the treatment requirement as soon as possible.
Example 2
As shown in FIG. 2, the nitrate nitrogen-containing waste liquid treatment apparatus of example 2 comprises an electrolytic separator 3, an electrolytic reaction tank partitioned into an anode region 1 and a cathode region 2 by the electrolytic separator 3, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, a first nitrogen oxide gas treatment apparatus 7, a tail gas treatment apparatus 21, and a waste liquid pretreatment tank 33. The electrolytic separator 3 is a cation exchange membrane; the first nitrogen oxide gas treatment device 7 is a nitrogen oxide gas normal temperature chemical reaction treatment device. The electrolysis anode 4 is positioned in the anode region 1 and is connected with the anode of the electrolysis power supply 6, and the electrolysis cathode 5 is positioned in the cathode region 2 and is connected with the cathode of the electrolysis power supply 6. The top of the cathode region 2 is provided with a first cover plate 9, and the first cover plate 9 is provided with a first air outlet 11 and a first feeding port 13. The first gas outlet 11 is connected to the first nitrogen oxide gas treatment device 7 through a second vacuum ejector 19. The top of the anode region 1 is provided with a second cover plate 10, and the second cover plate 10 is provided with a second air outlet 12; the second air outlet 12 is connected with a tail gas treatment device 21 through a first vacuum ejector 18. The anode region 1 is provided with a first impeller stirrer 15; the cathode region 2 is provided with a circulating liquid flow agitator 17. The waste liquid pretreatment tank 33 is connected with the first feeding port 13, and the waste liquid pretreatment tank 33 pretreats the waste liquid containing nitrate radicals and iron salts according to the requirements of table-1 to obtain an acidic catholyte, and feeds the acidic catholyte into the cathode region 2.
The device is used for treating the waste liquid containing nitrate radicals, and comprises the following specific steps:
the method comprises the following steps: preparing electrolyte according to the component proportion of the electrolyte in the anode region and the cathode region shown in the table-1, and adding the electrolyte into the anode region and the cathode region respectively; when the catholyte is prepared, firstly, inorganic base is put into the de-clamping waste liquid of the nitric acid type electroplating line for neutralization chemical reaction and is filtered, then the filtrate is obtained, and then sulfuric acid, ferric sulfate and ferric chloride are added into the filtrate to obtain the solution to be treated containing nitrate and ferric salt;
step two: immersing an electrolytic anode into the electrolyte in an electrolytic anode area of an electrolytic reaction tank and connecting the electrolytic anode with the anode of an electrolytic power supply, and immersing an electrolytic cathode into the electrolyte in an electrolytic cathode area of the electrolytic reaction tank and connecting the electrolytic cathode with the cathode of the electrolytic power supply;
step three: starting an electrolysis power supply to start the electrolyte to perform electrochemical reaction, and decomposing nitrate radical-containing liquid in an electrolysis cathode region;
step four: and (3) finishing the electrolysis operation, wherein the operation time is 24 hours, sampling and detecting the electrolyte in the electrolysis cathode region of the electrolysis reaction tank, and recording the detection result in the table-1.
During the electrolysis process, the pH value variation of the catholyte is manually monitored according to the table-1, the acidic catholyte is added into the cathode region in time, and the acidic substances in the waste liquid are utilized to ensure that iron hydroxide cannot be separated out from the catholyte. Oxygen is separated out from the anode area in the electrolysis process, nitrate radicals in the cathode area react chemically and produce nitric oxide gas. And the nitrogen monoxide gas is treated by a nitrogen oxide gas normal-temperature chemical reaction treatment device to generate nitrogen and is discharged.
Example 3
As shown in FIG. 3, the nitrate nitrogen containing waste liquid treatment apparatus of example 3 comprises an electrolytic divider 3, an electrolytic reaction tank partitioned into an anode section 1 and a cathode section 2 by the electrolytic divider 3, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, a first nitrogen oxide gas treatment apparatus 7, a second nitrogen oxide gas treatment apparatus 8, and a third nitrogen oxide gas treatment apparatus 34. The electrolytic separator 3 is a cation exchange membrane. The electrolysis anode 4 is positioned in the anode region 1 and is connected with the anode of the electrolysis power supply 6, and the electrolysis cathode 5 is positioned in the cathode region 2 and is connected with the cathode of the electrolysis power supply 6. The top of the cathode region 2 is provided with a first cover plate 9, and the first cover plate 9 is provided with a first air outlet 11 and a first feeding port 13. The first air outlet 11 is connected with the first nitrogen oxide gas treatment device 7 through a second vacuum ejector 19; the gas outlet of the first nitrogen oxide gas treatment device 7 is connected with the second nitrogen oxide gas treatment device 8 through a third vacuum ejector 20; the gas outlet of the second nitrogen oxide gas treatment device 8 is connected with a third nitrogen oxide gas treatment device 34. The first nitrogen oxide gas treatment device 7 and the second nitrogen oxide gas treatment device 8 are nitrogen oxide gas normal temperature chemical reaction treatment devices, and the third nitrogen oxide gas treatment device 34 is a nitrogen oxide gas high temperature reduction treatment device. The cathode section 2 is connected to a first replenisher reservoir 27 via a first feed opening 13.
The top of the anode region 1 is provided with a second cover plate 10, and the second cover plate 10 is provided with a second gas outlet 12 and a second feeding port 14. The second air outlet 12 is connected with a tail gas treatment device 21 through a first vacuum ejector 18. Anode region 1 is connected to a second replenisher reservoir 28 via second feed opening 14.
A first impeller stirrer 15 and a first electrolyte detection device 35 are arranged in the anode region 1; the cathode region 2 is provided with a second impeller stirrer 16, a cold-heat exchanger 30 and a second electrolyte detection device 36.
The device is used for treating the waste liquid containing nitrate radicals, and comprises the following specific steps:
the method comprises the following steps: preparing electrolyte according to the proportion of each component of the electrolyte in the anode region and the cathode region shown in the table-1, and adding the prepared electrolyte into the anode region and the cathode region respectively; when preparing the catholyte, firstly adding inorganic base into nitric acid-containing tin stripping water for neutralization chemical reaction, filtering, taking the filtrate, and adding ferrous chloride, ferrous sulfate and hydrochloric acid into the filtrate to obtain a solution to be treated containing nitrate and ferric salt;
step two: immersing an electrolytic anode into the electrolyte in the anode region and connecting the electrolytic anode with the anode of an electrolytic power supply, and immersing an electrolytic cathode into the electrolyte in the cathode region and connecting the electrolytic cathode with the cathode of the electrolytic power supply;
step three: starting an electrolytic power supply to start electrochemical reaction on the electrolyte, and treating the nitrate radical-containing liquid in the cathode region; in the electrolytic process, the catholyte prepared according to the table-1 is used for manually monitoring the change of the pH value of the solution in a cathode electrolytic cell area, and the acidic catholyte supplement is added into the electrolytic cathode cell area in time.
Step four: the electrolysis was completed for 18 hours, and the electrolyte in the electrolytic cathode region of the electrolytic reaction cell was sampled and examined, and the results of the examination are recorded in Table-1. In the electrolysis process, the change of the pH value of the catholyte is monitored, and an acidic catholyte supplement, namely a mixed solution of sulfuric acid and hydrochloric acid, is added into a cathode area in time to maintain the solution without precipitating iron hydroxide. Oxygen is separated out from the anode area in the electrolysis process, and prepared anolyte is continuously supplemented to the anode area from the second supplement storage tank according to the process requirements; and nitrate radicals in the cathode region react to produce nitrogen oxide gas, and the separated nitrogen oxide gas is treated by a multistage series nitrogen oxide gas treatment device to generate nitrogen and is discharged.
Example 4
The device of FIG. 3 is used for treating the waste liquid containing nitrate radicals, and the specific steps are as follows:
the method comprises the following steps: preparing electrolyte according to the proportion of each component of the electrolyte in the anode region and the cathode region shown in the table-1, and adding the prepared electrolyte into the anode region and the cathode region respectively; when preparing the catholyte, firstly, putting a metal ion complexing agent into the nitrate-containing metal plating solution waste liquid for metal ion chemical complexing reaction, producing a complex precipitate by the reaction, filtering the complex precipitate, taking a filtrate, and adding sulfuric acid and ferrous sulfate into the filtrate to obtain a to-be-treated liquid containing nitrate and ferric salt;
step two: immersing an electrolytic anode into the electrolyte in the anode region and connecting the electrolytic anode with the anode of an electrolytic power supply, and immersing an electrolytic cathode into the electrolyte in the cathode region and connecting the electrolytic cathode with the cathode of the electrolytic power supply;
step three: starting an electrolysis power supply to start electrochemical reaction on the electrolyte, and treating nitrate radical-containing liquid in an electrolysis cathode area;
step five: after the electrolysis operation is finished and the operation time is 10 hours, sampling and detecting the electrolyte in the electrolysis cathode area of the electrolysis reaction tank, and recording the detection result in table-1.
During the electrolysis process, the change of the pH value of the catholyte is monitored, and an acid catholyte supplement, namely a sulfuric acid solution, is added into the cathode area in time to maintain the solution without separating out iron hydroxide. Oxygen is separated out from the anode area in the electrolysis process, and prepared anolyte and/or water are continuously supplemented to the anode area from the second supplement storage tank according to the process requirements; during which time iron ions in the anolyte migrate through the electrolytic separator into the cathode region. Meanwhile, nitrate radicals in the cathode region react chemically to produce nitrogen oxide gas, and the separated nitrogen oxide gas is processed by a multistage nitrogen oxide gas processing device connected in series to generate nitrogen and then discharged.
Example 5
As shown in FIG. 4, the apparatus for treating a nitrate nitrogen-containing waste liquid according to example 5 comprises an electrolytic separator 3, an electrolytic reaction tank partitioned into an anode region 1 and a cathode region 2 by the electrolytic separator 3, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, a first nitrogen oxide gas treatment apparatus 7, and a tail gas treatment apparatus 21. The electrolytic separator 3 is a cation exchange membrane, and the first nitrogen oxide gas treatment device 7 is a nitrogen oxide high-temperature reduction treatment device. The electrolysis anode 4 is positioned in the anode region 1 and is connected with the anode of the electrolysis power supply 6, and the electrolysis cathode 5 is positioned in the cathode region 2 and is connected with the cathode of the electrolysis power supply 6.
The top of the cathode area 2 is provided with a first cover plate 9, and the first cover plate 9 is provided with a first air outlet 11, a first feeding port 13 and a second feeding port 14. The first gas outlet 11 is connected with the first nitrogen oxide gas treatment device 7 through a first nitrogen oxide gas analysis detector 31; the gas outlet of the first nitrogen oxide gas treatment device 7 is provided with a second nitrogen oxide gas analysis detector 32. The first feeding port 137 is connected with a first supplement storage tank 27 through a pump P5, and the first supplement storage tank stores acid cathode electrolyte supplement; second feed opening 14 is connected to catholyte preparation tank 24 via pump P4, which serves to store catholyte. The cathode area 2 is connected with a first transfer tank 25 for storing overflow liquid of the cathode area. The cathode region 2 is also provided with a circulating flow agitator 17 and a second electrolyte detection means 36.
The top of the anode region 1 is provided with a second cover plate 10, and the second cover plate 10 is provided with a second air outlet 12 and a third feeding port 37. The tail gas treatment device 21 is connected with the second gas outlet 12 through the first vacuum ejector 18. The third feed opening 37 is connected to a third replenisher storage tank 38 via a pump P2 for storing the prepared anolyte. The anode region 1 is connected with a third transfer tank 39 for storing overflow liquid of the anode region. The cathode region 1 is further provided with a first impeller stirrer 15 and a first electrolyte detection device 35.
The apparatus for treating a nitrate nitrogen-containing waste liquid according to embodiment 6 further includes an automatic feed controller 29; the signal output end of the automatic feeding controller 29 is connected with the signal input ends of the pumps P2, P4, P5 and the electrolysis power supply; the signal input end of the automatic feeding controller 29 is connected with the signal output ends of the first nitrogen oxide gas analysis detector 31, the second nitrogen oxide gas analysis detector 32, the first electrolyte detection device 35 and the second electrolyte detection device 36.
The device is used for treating the waste liquid containing nitrate radicals, and comprises the following specific steps:
the method comprises the following steps: preparing electrolyte according to the component proportions of the electrolyte in the anode region and the electrolyte in the cathode region shown in the table-1, and adding the prepared electrolyte into the anode region and the cathode region respectively; when preparing the catholyte, firstly, sulfuric acid is put into the nitrate radical-containing alkaline electroplating waste liquid for neutralization chemical reaction and is filtered, then the filtrate is obtained, and ferrous chloride and ferric chloride are added into the acidic filtrate to obtain the nitrate radical-containing and ferric salt-containing solution to be treated;
step two: immersing an electrolytic anode into the electrolyte in the anode region and connecting the electrolytic anode with the anode of an electrolytic power supply, and immersing an electrolytic cathode into the electrolyte in the cathode region and connecting the electrolytic cathode with the cathode of the electrolytic power supply;
step three: starting an electrolytic power supply to start electrochemical reaction on the electrolyte, and treating the nitrate radical-containing liquid in the cathode region;
step four: after the electrolysis operation is finished, the operation time is 5 hours, the electrolyte in the electrolysis cathode area of the electrolysis reaction tank is sampled and detected, and the detection result is recorded in the table-1.
In the electrolytic process, nitrate radicals in a cathode region react chemically and generate nitric oxide gas, the device is monitored by an oxidation-reduction potentiometer and an acidity meter, wherein each electrolyte detection device and each nitric oxide gas analysis detector perform sampling detection to send data to an automatic detection feeding controller for processing, the automatic detection feeding controller respectively controls executing elements such as a pump P2, a pump P4, a pump P5, an electrolytic power supply and the like according to processing results, so that the pH value and the oxidation-reduction potential variation of a solution in the cathode region are monitored by the automatic detection feeding controller, an acidic cathode electrolyte supplement and a cathode electrolyte are timely added into the cathode region, and the acidic cathode electrolyte supplement is a sulfuric acid solution and/or a waste liquid to be processed containing nitrate radicals and iron salts; and detecting parameters such as liquid level and electrolyte concentration in the anode region, and replenishing the anolyte in time. And meanwhile, nitrogen gas is generated and discharged after the nitrogen oxide gas precipitated in the cathode area is treated by the nitrogen oxide gas high-temperature reduction treatment device, the discharged gas is monitored by a nitrogen oxide gas analysis detector, and the output current of the electrolytic power supply is adjusted according to the result measured by the nitrogen oxide gas analysis detector.
Example 6
As shown in FIG. 5, the nitrate nitrogen-containing waste liquid treatment apparatus of example 6 comprises an electrolytic separator 3, an electrolytic reaction tank partitioned into an anode region 1 and a cathode region 2 by the electrolytic separator 3, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, and a first nitrogen oxide gas treatment apparatus 7. The electrolytic separator 3 is a cation exchange membrane. The electrolysis anode 4 is positioned in the anode region 1 and is connected with the anode of the electrolysis power supply 6, and the electrolysis cathode 5 is positioned in the cathode region 2 and is connected with the cathode of the electrolysis power supply 6. The top of the cathode area 2 is provided with a first cover plate 9, and the first cover plate 9 is provided with a first air outlet 11, a first feeding port 13 and a second feeding port 14. The first air outlet 11 is connected with a first nitrogen oxide gas treatment device 7 through a second vacuum ejector 19, and the first nitrogen oxide gas treatment device 7 is a nitrogen oxide gas normal-temperature chemical reaction treatment device. The cathode area 2 is connected with a first transfer tank 25 through a first feeding port 13 to form a loop; a cold-hot temperature exchanger 30 is arranged in the first transit tank 25 and is connected with a cathode electrolyte preparation tank 24 through a feed port; catholyte preparation tank 24 is connected to a first replenisher storage tank 27 via solids dosing equipment 44 and to a second transit tank 26 via pumps and valves; the second transit tank 26 is connected with a third transit tank 39 through a feeding port; the third transit tank 39 is connected with a COD detector 48 and a water-oil separator 22 in sequence; the water-oil separator 22 is connected with a fourth transit tank 40 and a fifth transit tank 41 respectively; the fourth transit tank 40 and the fifth transit tank 41 are connected to the first solid-liquid separator 23 in common; the first solid-liquid separator 23 is connected to a sixth transit tank 42; the sixth transit tank 42 is connected with a waste liquid pretreatment tank 33 through a feed inlet; the reject pretreatment tank 33 is connected to a second extender storage tank 28 by a second solids dosing device 47. The cathode section 2 is connected to a fourth replenisher reservoir 49 through the second inlet 14.
The top of the anode region 1 is provided with a second cover plate 10, and the second cover plate 10 is provided with a second gas outlet 12 and a third feeding port 37. The second air outlet 12 is connected with a tail gas treatment device 21 through a first vacuum ejector 18. The anode section 1 is connected with a seventh transfer tank 43 through a third feeding port 37 to form a loop, and the seventh transfer tank 43 is connected with a third supplement storage tank 38 through a feeding port.
A first impeller stirrer 15 and a first electrolyte detection device 35 are arranged in the anode region 1, and a second solid-liquid separator 45 is connected with the anode region through a circulating pipeline; the cathode region 2 is provided with a second impeller stirrer 16, a cold/hot temperature exchanger 30 and a second electrolyte detection device 36, and is connected to a third solid-liquid separator 46 through a circulation pipe.
The electrolytes in the anode and cathode regions shown in Table-1 were mixed in the proportions of the components, and the procedure of example 4 was repeated to treat the nitrate-containing waste liquid. The electrolysis was completed for 18 hours, and the electrolyte in the electrolytic cathode region of the electrolytic reaction cell was sampled and examined, and the results of the examination are recorded in Table-1.
In the electrolytic process, the change of the pH value of the catholyte is monitored, and an acid catholyte supplement, namely a mixed solution of sulfuric acid and hydrochloric acid, is added into a cathode region in time. The acidic catholyte is prepared in a catholyte preparation tank after being pretreated in a waste liquid pretreatment tank and passing through a solid-liquid separator and a water-oil separator. Oxygen is separated out from the anode area in the electrolysis process, and prepared anolyte is continuously supplemented from a third supplementing storage tank to a seventh transfer tank which is circularly connected with the anode area according to the process requirements; and nitrate radicals in the cathode region react to produce nitrogen oxide gas, and the precipitated nitrogen oxide gas is treated by a nitrogen oxide gas treatment device to generate nitrogen and then is discharged.
Example 7
The electrolytes in the anode and cathode regions shown in Table-1 were mixed in the proportions of the components thereof, and the nitrate-containing waste liquid was treated by repeating the procedure of example 6 using the same nitrate-containing waste liquid treatment apparatus as that of example 6. The electrolysis was completed for 18 hours, and the electrolyte in the electrolytic cathode region of the electrolytic reaction cell was sampled and examined, and the results of the examination are recorded in Table-1.
TABLE-1
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above embodiments of the present invention should be considered as illustrative and not restrictive. Therefore, any slight modifications, equivalent changes and modifications made to the above embodiments according to the actual technology of the present invention are all within the scope of the technical solution of the present invention.
Claims (14)
1. An apparatus for treating a nitrate-containing waste liquid, comprising: comprises an electrolytic reaction tank, an electrolytic separator, an electrolytic anode, an electrolytic cathode, an electrolytic power supply, a nitrogen oxide gas treatment device and a supplement storage tank; the electrolytic separator divides the electrolytic reaction tank into an anode region and a cathode region; the top of the cathode area is provided with a first cover plate with an air outlet, and the air outlet of the first cover plate is connected with the nitrogen oxide gas treatment device; the supplement storage tank is used for containing supplements to be added to the anode region or the cathode region and is connected with the anode region or the cathode region; the electrolytic separator is a material which can separate the electrolytic reaction tank and effectively prevent anions in the catholyte from migrating to the anolyte under the action of an electric field.
2. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 1, wherein: the nitrogen oxide gas treatment device is one or more of a commercially available nitrogen oxide gas normal-temperature chemical reaction treatment device and a glowing metal high-temperature reduction nitrogen oxide gas treatment device consisting of a catalytic metal placing cavity and a heating device.
3. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 2, wherein: a pumping device is arranged between the gas outlet of the first cover plate and the nitrogen oxide gas treatment device or between the nitrogen oxide gas treatment devices connected in series in multiple stages and is used for accelerating the pumping and discharging of tail gas from a cathode area or the nitrogen oxide gas treatment device; the pumping device is an air pump or a vacuum ejector; the treatment device comprises a nitrogen oxide gas analysis detector arranged at the gas outlet of the cathode region or the gas outlet of the nitrogen oxide gas treatment device.
4. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 1, wherein: the electrolysis power supply is provided with a current regulator or is connected with the current regulator and is used for regulating the current output by the electrolysis power supply according to the electrolysis condition or controlling the on or off of the electrolysis power supply; the electrolysis power supply adopts a pulse type electrolysis power supply.
5. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 1, wherein: the anode region and/or the cathode region are/is provided with an electrolyte detection device; the electrolyte detection device comprises at least one detection device of a liquid level meter, a hydrometer, an acidimeter, an oxidation-reduction potentiometer, a photoelectric colorimeter, a thermometer and a pH meter.
6. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 1, wherein: the treatment device comprises a cathode electrolyte preparation tank for preparing and temporarily storing the cathode electrolyte to be subjected to electrolytic treatment; the catholyte preparation tank is connected with the cathode region.
7. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 6, wherein: the treatment device comprises a waste liquid pretreatment tank for pretreating waste liquid; the waste liquid pretreatment tank is connected with the cathode electrolyte preparation tank or the cathode area.
8. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 7, wherein: the treatment device comprises a solid-liquid separator for carrying out solid-liquid separation on the treatment liquid with solid precipitates or the treatment liquid with solids separated out in the treatment process; the solid-liquid separator is arranged between any two similar or dissimilar tanks in the catholyte preparation tank, the waste liquid pretreatment tank and the cathode region, or is connected with one of the cathode region and the anode region to form a loop.
9. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 8, wherein: the treatment device comprises a water-oil separator, and the water-oil separator is used for carrying out water-oil separation pretreatment on the waste liquid containing nitrate radicals or the pretreated waste liquid and is arranged between any two similar or dissimilar tanks in the cathode electrolyte preparation tank, the waste liquid pretreatment tank and the cathode area.
10. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 9, wherein: the treatment device comprises a transfer tank for storing a solution to be treated or in the treatment process; the transfer tank is arranged between any two of the same type or different types of the catholyte preparation tank, the waste liquor pretreatment tank, the cathode region, the solid-liquid separator and the water-oil separator, or is connected with one of the catholyte preparation tank, the waste liquor pretreatment tank, the cathode region and the anode region; when a plurality of transit tanks are employed at the same position, the transit tanks may be arranged in parallel or in series.
11. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 10, wherein: the replenisher storage tank is connected with one of an anode region, a cathode region, a catholyte preparation tank, a waste liquid pretreatment tank and a transit tank connected with the anode region or the cathode region through a feeding pump or solid feeding equipment.
12. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 10, wherein: the treatment device comprises a cold-hot temperature exchanger which is arranged in at least one of the anode region, the cathode region and a transit tank connected with the anode region or the cathode region and used for adjusting the temperature of the electrolyte in the anode region or the cathode region.
13. The apparatus for treating a nitrate nitrogen-containing waste liquid according to any one of claims 3, 4, 5, 11 and 12, wherein: the processing device comprises an automatic feeding controller, the signal output end of the automatic feeding controller is connected with the signal input end of at least one of a feeding pump, a solid feeding device, a pumping and discharging device, a current regulator and a cold-hot temperature exchanger, and the automatic feeding controller controls the operation of the device connected with the signal output end of the automatic feeding controller according to a time program and/or a detection result of an electrolyte detection device and/or a nitrogen oxide gas analysis detector; and the signal input end of the automatic feeding controller is connected with the signal output end of at least one of the electrolyte detection device and the nitrogen oxide gas analysis detector.
14. The apparatus for treating a nitrate nitrogen-containing waste liquid according to claim 9, wherein: the treatment device comprises a COD detector for monitoring COD of the liquid passing through the water-oil separator; the COD detector is arranged in a flow pipeline of liquid obtained after the treatment of the water-oil separator.
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