CN112723585B - Hypophosphite treatment reactor for realizing iodine recycling, and facility and method thereof - Google Patents
Hypophosphite treatment reactor for realizing iodine recycling, and facility and method thereof Download PDFInfo
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- CN112723585B CN112723585B CN202011338714.5A CN202011338714A CN112723585B CN 112723585 B CN112723585 B CN 112723585B CN 202011338714 A CN202011338714 A CN 202011338714A CN 112723585 B CN112723585 B CN 112723585B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- 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
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- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a hypophosphite treatment reactor for realizing iodine recycling, and facilities and a method thereof.A blocking device and a blocking support plate of the reactor divide an inner cavity into a water inlet area, a reaction area and a water outlet area along the axial direction; active carbon particles for adsorbing iodine simple substances are filled in the middle lower part of the reaction zone to form a reaction bed, and a plurality of vertical air pipes are also arranged in the reaction zone; the air compressor can lead air into the air pipe through the air inlet pipe, so that negative pressure is formed near the air inlet at the bottom end of the air pipe, and waste liquid and activated carbon particles near the air inlet are pumped into the air pipe under pressure difference, rise to the air outlet at the top end and overflow, and fall back to the reaction bed under the action of gravity. According to the invention, the air compressor is periodically started, so that the activated carbon particles losing the iodine elementary substance at the lower part of the reaction bed are turned over to the upper part to adsorb the iodine elementary substance again, and the iodine elementary substance is prevented from being separated from the reaction bed in the water flow migration process to cause loss.
Description
Technical Field
The invention belongs to the field of complex heavy metal wastewater treatment, and particularly relates to a hypophosphite treatment reactor for realizing iodine recycling, and facilities and a method thereof.
Background
The chemical nickel plating solution mainly comprises nickel salt, complexing agent, reducing agent and additive. Nickel salt is the main salt of the plating solution, and generally used are nickel sulfate, nickel chloride, nickel acetate, nickel carbonate and the like; the complexing agent is added into the plating solution to ensure that nickel ions generate stable complex and can prevent the generation of hydroxide and phosphite; the reducing agent is generally sodium hypophosphite which has the function of providing active hydrogen atoms through catalytic dehydrogenation to reduce nickel ions into metallic nickel.
The huge chemical plating industry is helpful for the rapid development of modern industry and brings serious environmental pollution problem, and the chemical plating bath solution which is scrapped periodically usually has the characteristics of complex pollutant components, high concentration, toxicity, harm, high treatment difficulty and the like, and contains high-concentration refractory organic matters and inorganic salts besides high-concentration heavy metals. For example, hypophosphite is commonly treated by methods such as chemical precipitation, electrodialysis, microelectrolysis, advanced oxidation and the like in the main oxidation process for removing hypophosphite in the existing chemical nickel plating solution, and hypophosphite is oxidized into orthophosphate and then reacts with calcium ions or iron ions to generate precipitates for removal. In fact, phosphite can also react with calcium ions or iron ions to generate precipitates for removal, but the existing oxidation process of hypophosphite directly oxidizes the phosphite into orthophosphate, so that the oxidation process has no selectivity, the treatment cost is high, and the oxidation of the hypophosphite is incomplete.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hypophosphite treatment reactor for realizing iodine recycling, and a facility and a method thereof.
The invention adopts the following specific technical scheme:
a hypophosphite treatment reactor for realizing iodine recycling comprises a shell, an upper end enclosure, an interception device, an interception support plate and a plurality of air pipes;
the upper end enclosure is fixed at the top of the shell, and the upper end enclosure and the shell jointly form a closed reactor with an inner cavity; the bottom of the reactor is provided with a water inlet, and the top of the reactor is provided with a water outlet; the intercepting device is fixed at the upper part of the inner cavity, the intercepting support plate provided with a plurality of holes is fixed at the lower part of the inner cavity, and the intercepting device and the intercepting support plate respectively and completely cover the cross section of the inner cavity; the inner cavity is axially divided into a water inlet area, a reaction area and a water outlet area by the intercepting device and the intercepting support plate; after the waste liquid enters the inner cavity of the reactor, the waste liquid can only enter the water outlet area after being treated by the reaction area from the water inlet area;
activated carbon particles for adsorbing iodine simple substances are filled in the middle lower part of the reaction zone to form a reaction bed, and a plurality of vertical air pipes are arranged in the reaction zone; the top end of the air pipe extends out of the reaction bed and is lower than the interception device, a suspension interval is arranged between the bottom end of the air pipe and the interception supporting plate, and an air inlet pipe is coaxially sleeved in an air cavity positioned at the bottom of the air pipe; one end of the air inlet pipe extends into the air pipe from the air inlet and keeps a distance with the air pipe, and the other end of the air inlet pipe is connected with an air compressor which is positioned outside the reactor and used for supplying air; the air compressor can lead air into the air pipe through the air inlet pipe, so that negative pressure is formed near the air inlet at the bottom end of the air pipe, waste liquid and active carbon particles near the air inlet are pumped into the air pipe under pressure difference, ascend to the air outlet at the top end and overflow, and fall back to the reaction bed under the action of gravity.
Preferably, the upper end enclosure is detachably fixed at the top of the shell, and the interception device is detachably fixed at the upper part of the inner cavity of the reactor.
Preferably, the shell in which the reaction zone is located is of a cylindrical structure.
Preferably, the interception supporting plate is a pore plate uniformly provided with a plurality of holes, and one side of the interception supporting plate, which is in contact with the reaction bed, is provided with an interception net for preventing activated carbon particles from leaking; the interception device is an interception net.
Preferably, the plurality of gas pipes are uniformly distributed in the reaction zone.
The second purpose of the invention is to provide a hypophosphite treatment facility for realizing iodine recycling, which comprises a coagulation air flotation unit, a sand filtration unit, a dosing unit and a reaction unit which are sequentially communicated through pipelines, wherein the reaction unit is formed by communicating a plurality of hypophosphite treatment devices as any one of the first purposes.
Preferably, as a second purpose, the reaction units are multiple and operate in parallel; several of the hypophosphite treatment devices in each reaction unit operate in series.
Preferably, the coagulation air flotation unit is a coagulation air flotation tank, the sand filtration unit is a sand filter tank, and the medicine adding unit is a reaction tank for adjusting the pH value of the wastewater and adding hydrogen peroxide.
The third purpose of the invention is to provide a method for removing hypophosphite from chemical nickel plating waste liquid by using the hypophosphite treatment facility based on any one of the second purpose, which comprises the following specific steps:
introducing the chemical nickel plating waste liquid to be treated into a coagulation air floatation unit, and forming flocs by the suspended matters in the waste liquid and an air floatation flocculating agent added into the coagulation air floatation unit through flocculation; meanwhile, orthophosphate in the wastewater reacts with the air flotation flocculant to generate insoluble suspended matters; the insoluble suspended matters and the flocs rise to the water surface under the aeration action of an aeration device in the coagulation air flotation unit to form suspended scum; the suspended floating slag is scraped under the action of a slag scraper, so that solid-liquid separation is realized to further remove impurities and macromolecular organic matters in the wastewater;
the waste liquid treated by the coagulation air flotation unit enters a sand filtration unit, and insoluble solid impurities in the waste liquid are intercepted and removed from the waste liquid;
the waste liquid treated by the sand filtration unit enters a dosing unit, the pH value is adjusted to 1.6-1.8, and then the waste liquid is mixed with hydrogen peroxide to obtain pretreated waste water, and the pretreated waste water is introduced into a reaction unit;
the pretreated wastewater slowly flows through a water inlet area of the hypophosphite treatment device and then enters a reaction area, hypophosphite in the pretreated wastewater is oxidized into phosphite by iodine simple substances, the iodine simple substances are reduced into iodine ions, the reduced iodine ions are oxidized into the iodine simple substances by hydrogen peroxide, and the iodine simple substances are adsorbed by activated carbon particles again to realize repeated use; the wastewater treated by the reaction zone flows out of the phosphate treatment device from a water outlet through a water outlet zone; then, adding calcium ions or iron ions into phosphite in the wastewater to react with the phosphite to generate precipitate so as to remove the phosphite in the wastewater;
the air compressor is periodically started, air is introduced into the air pipe through the air inlet pipe through the air compressor, a negative pressure state is formed near the air inlet at the bottom end of the air pipe, waste water and active carbon particles near the air inlet are pumped into the air pipe under the pressure difference and ascend to the air outlet at the top end to be discharged out of the air pipe, and then the waste water and the active carbon particles fall back to the reaction bed under the action of gravity, so that the active carbon particles losing iodine simple substances at the lower part of the reaction bed are turned over to the upper part to adsorb the iodine simple substances again, and the iodine simple substances are prevented from being separated from the reaction bed along with the water flow migration process to cause loss.
Preferably, for the third purpose, the adding amount of the hydrogen peroxide is 11.5-14 mL/g hypophosphite (counted by P), and the mass fraction of the hydrogen peroxide is 30%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention can control the hypophosphite in the waste liquid to be converted into phosphite instead of orthophosphate, greatly reduce the dosage of the oxidation medicament and reduce the treatment cost, and the oxidation process has high selectivity and high oxidation efficiency.
(2) The consumed medicament adopted in the invention is mainly hydrogen peroxide, hydrogen ions generated in the reaction process are balanced with the consumed hydrogen ions, no acid or alkali is added in the reaction process, and the process operation is simple and convenient to control.
(3) The invention has no iodine loss in the whole operation process, so that the activated carbon particles and the iodine do not need to be replaced or supplemented.
(4) Because of the characteristics of the process, the iodine elementary substances adsorbed in the activated carbon particles can inevitably migrate upwards slowly along with the continuous operation of the reactor, so that the activated carbon particles losing the iodine elementary substances at the lower part of the reaction bed are turned over to the upper part to adsorb the iodine elementary substances again by periodically starting the air compressor, and the iodine elementary substances are prevented from separating from the reaction bed in the water flow migration process to cause loss.
(5) The invention greatly reduces the pollution and the dirt blockage of the reaction bed through the pretreatment of the inlet water and prolongs the service life of the active carbon particles in the reaction bed.
Drawings
FIG. 1 is a schematic view of the structure of a hypophosphite treatment reactor according to the present invention;
FIG. 2 is a schematic view of the structure of a hypophosphite treatment facility according to the present invention;
the reference numbers in the figures are: 1 coagulation air flotation unit, 2 sand filtration unit, 3 dosing unit, 4 reaction unit, 41 shell, 42 upper end enclosure, 43 interception device, 44 air pipe, 45 interception supporting plate, 46 air inlet pipe and 47 air compressor.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
As shown in fig. 1, the present invention provides a hypophosphite treatment reactor for realizing iodine recycling, which comprises a shell 41, an upper sealing head 42, an interception device 43, an interception support plate 45 and a plurality of air pipes 44.
The upper end enclosure 42 is fixed to the top of the shell 41, and the upper end enclosure 42 and the shell 41 together form a closed reactor with an inner cavity. The bottom of the reactor is provided with a water inlet, and the top of the reactor is provided with a water outlet. The interception device 43 is fixed on the upper part of the inner cavity of the reactor, the interception supporting plate 45 is fixed on the lower part of the inner cavity of the reactor, and the interception device 43 and the interception supporting plate 45 respectively and completely cover the cross section of the inner cavity where the interception device is located. The reactor interior is axially divided into successive inlet, reaction and outlet zones by the interceptor unit 43 and interceptor support plate 45. After the waste liquid enters the inner cavity of the reactor, the waste liquid can only enter the water outlet area after being treated by the reaction area from the water inlet area. In practical application, the intercepting device 43 may be set as an intercepting net; the interception supporting plate 45 may be provided with a perforated plate having a plurality of holes, and an interception net capable of completely covering the interception supporting plate 45 is disposed at a side of the interception supporting plate 45 contacting the reaction bed. Because the middle-lower part of the reaction zone is filled with the activated carbon particles which adsorb the iodine simple substance to form a reaction bed, the holes of the interception device 43 and the interception supporting plate 45 are not too large, thereby achieving the purpose of effectively preventing the activated carbon particles from leaking.
A plurality of vertical air pipes 44 are uniformly arranged in the reaction zone, the top ends of the air pipes 44 extend out of the reaction bed and are lower than the interception device 43, the bottom ends of the air pipes 44 are positioned above the interception supporting plate 45 and have a suspension interval with the interception supporting plate 45, and air inlet pipes 46 are coaxially sleeved in air cavities at the bottoms of the air pipes 44. One end of the air inlet pipe 46 extends into the air pipe 44 from the air inlet and keeps a distance with the air pipe 44, and the other end is connected with an air compressor 47 which is positioned outside the reactor and used for supplying air. The air compressor 47 can introduce high-pressure air into the air pipe 44 through the air inlet pipe 46, so that a negative pressure state is formed near the air inlet at the bottom end of the air pipe 44, and waste liquid and activated carbon particles near the air inlet are pumped into the air pipe 44 under the pressure difference and ascend to the air outlet at the top end of the air pipe 44 to overflow, and then fall back to the upper part of the reaction bed under the action of gravity. In practical applications, the cross-sectional dimension of the air tube 44 should be larger than that of the air inlet tube 46, and the air tube and the air inlet tube are coaxially sleeved to form an annular space, so that the waste liquid and the activated carbon particles near the air inlet of the air tube 44 can be sucked into the air tube 44 from the annular space under the pressure difference and ascend to the top end of the air tube 44.
In practical applications, the upper cap 42 can be detachably fixed on the top of the shell 41, and the interception device 43 can be detachably fixed on the upper portion of the inner cavity of the reactor. This arrangement may facilitate periodic opening of the upper head 42 and the interceptor 43 to replace the blocked air tube 44 or to backwash the blocked air tube 44.
In practical application, the shape and structure of the shell 41 and the upper end enclosure 42 can be controlled, so that the reactor formed by the shell 41 and the upper end enclosure 42 is a cylindrical structure with two gradually reduced ends, that is, along the water flow direction, the reaction cavity where the water inlet area is located is a gradually enlarged structure, the reaction cavity where the reaction area is located is a cylindrical structure, and the reaction cavity where the water outlet area is located is a gradually reduced structure.
The preparation method of the activated carbon particles for adsorbing iodine elementary substances comprises the following steps:
preparing iodine simple substance into iodine solution with the concentration of c, and adding the iodine solution with the volume of V 1 Stirring and mixing the active carbon particles with the particle size of 0.5-1 cm until the supernatant has no free iodine simple substance, stirring for 2-5 h, and filtering to obtain active carbon particles adsorbing the iodine simple substance;
volume V of activated carbon granules 1 It is calculated by the following formula,
m 2 ＝Q×c′×T
V 1 ＝m 1 /ρ
wherein m is 2 The mass of hypophosphite (calculated as P) in the waste liquid is in mg; q is inflow rate in m 3 H; c' is the concentration of hypophosphite (in terms of P) in the waste liquid, and the unit is mg/m 3 (ii) a T is the running time of the reactor and the unit is h; m is 1 The unit is the mass of the activated carbon particles, and is g; v is the oxidation rate of hypophosphite, with the unit of mg hypophosphite (calculated as P)/(g activated carbon &), with a size ranging from 0.35 to 0.4; rho is the bulk density of the activated carbon particles and is expressed in g/m 3 ；V 1 Is the volume of activated carbon particles (i.e. reaction bed) in m 3 ；
Mass m of iodine in iodine solution 3 ≥0.061m 1 Volume V of iodine solution 2 ≥2V 1 The concentration c ═ m of iodine in the iodine solution 3 /V 2 (ii) a Wherein, V 2 Is the volume of the iodine solution in m 3 ；m 3 The unit is the mass of iodine in the iodine solution, and the unit is g; c concentration of iodine in iodine solution in g/m 3 。
As shown in fig. 2, the invention also provides a hypophosphite treatment facility for realizing iodine recycling, which comprises a coagulation air flotation unit 1, a sand filtration unit 2, a drug adding unit 3 and a reaction unit 4 which are sequentially communicated through a pipeline, wherein the coagulation air flotation unit 1 is a coagulation air flotation tank, the sand filtration unit 2 is a sand filtration tank, the drug adding unit 3 is a reaction tank for adjusting the pH of wastewater and adding hydrogen peroxide, and the reaction unit 4 is formed by communicating a plurality of hypophosphite treatment devices.
In the practical application process, in order to quickly and completely treat the wastewater flowing out of the dosing unit, a plurality of reaction units 4 can be arranged, all the reaction units 4 run in parallel, and each reaction unit 4 is internally provided with a plurality of hypophosphite treatment devices which run in series.
The method for removing hypophosphite from the chemical nickel plating waste liquid based on the hypophosphite treatment facility comprises the following specific steps:
firstly, introducing the chemical nickel plating waste liquid to be treated into a coagulation air flotation unit 1, and forming flocs through flocculation of suspended matters in the waste liquid and an air flotation flocculating agent added into the coagulation air flotation unit 1. Meanwhile, orthophosphate in the wastewater reacts with the air flotation flocculating agent to generate insoluble suspended matters. The insoluble suspended matters and the flocs rise to the water surface under the aeration action of an aeration device in the coagulation air flotation unit 1 to form suspended scum. The floating slag is scraped under the action of the slag scraper, so that solid-liquid separation is realized, and impurities and macromolecular organic matters in the wastewater are further removed.
The waste liquid treated by the coagulation air flotation unit 1 enters a sand filtration unit 2, the sand filtration unit 2 can adopt a filter tank using quartz sand as a filter material, large granular insoluble solid impurities in the waste liquid are removed through physical interception treatment, and a small part of COD can be removed at the same time.
And (3) feeding the waste liquid treated by the sand filtration unit 2 into a dosing unit 3, firstly adding hydrochloric acid into the waste liquid to adjust the pH value of the waste liquid to 1.6-1.8, then stopping adding the hydrochloric acid, adding hydrogen peroxide into the waste liquid with the adjusted pH value, and uniformly mixing the hydrogen peroxide and the waste liquid to obtain the pretreated waste water. The pretreated wastewater is then passed to reaction unit 4.
In the hypophosphite treatment device of the reaction unit 4, the pretreated wastewater slowly flows through a water inlet area of the hypophosphite treatment device and then enters a reaction area, hypophosphite in the pretreated wastewater is oxidized into phosphite by iodine simple substances, the iodine simple substances are reduced into iodine ions, the reduced iodine ions are oxidized into the iodine simple substances by hydrogen peroxide, and the iodine simple substances are adsorbed by active carbon particles again to realize reuse. The wastewater treated by the reaction zone flows out of the phosphate treatment device from the water outlet through the water outlet zone. And then, adding calcium ions or iron ions into the phosphite in the wastewater to react with the phosphite to generate precipitate, and removing the phosphite in the wastewater.
In the embodiment, the mass fraction of the hydrogen peroxide is 30%, and the adding amount is 11.5-14 mL/g hypophosphite counted by P. The concentration of hypophosphite in P in the chemical nickel plating waste liquid is less than 1500mg/L, and the concentration of suspended matters in P in the chemical nickel plating waste liquid is less than 200 mg/L.
The air compressor 47 is periodically started, air is introduced into the air pipe 44 through the air inlet pipe 46 through the air compressor 47, a negative pressure state is formed near an air inlet at the bottom end of the air pipe 44, waste water and active carbon particles near the air inlet are pumped into the air pipe 44 under the pressure difference and ascend to an air outlet at the top end, the waste water and the active carbon particles are discharged out of the air pipe 44, the waste water and the active carbon particles fall back to the reaction bed under the action of gravity, the active carbon particles losing iodine simple substances at the lower part of the reaction bed are enabled to be overturned to move to the upper part to re-adsorb the iodine simple substances, and therefore the iodine simple substances are prevented from being separated from the reaction bed along with the water flow migration process to cause loss.
Examples
In the embodiment, the device and the method are adopted to treat the chemical nickel plating waste liquid separately collected in a sewage treatment plant in a certain electroplating park. Wherein the daily treated water amount is 40t, the hypophosphite content is 480mg/L, and the device operation time is 12 h/d.
The chemical nickel plating waste liquid to be treated is firstly pretreated by a coagulation air flotation unit and a sand filtration unit, impurities and macromolecular organic matters in the waste liquid are intercepted and removed, and then the chemical nickel plating waste liquid is mixed with hydrogen peroxide after the pH value is adjusted in a dosing unit to obtain the pretreated waste water. Introducing the pretreated wastewater into a reaction unit.
The reaction units are arranged into two groups which are operated in parallel, each group of reaction units is provided with three reactors connected in series, the diameter of each reactor is 1m, the reaction zone is uniformly filled with activated carbon particles to form a reaction bed, and the height of the reaction bed is 2.5 m. Two air pipes are arranged in each reactor, an air inlet pipeline externally connected with the two air pipes is provided with a self-control valve, air is regularly introduced through the self-control valve every day, so that activated carbon particles losing elemental iodine at the lower part of the reaction bed are turned to the upper part to adsorb the elemental iodine again, and the elemental iodine is prevented from being separated from the reaction bed along with the water flow in the migration process to cause loss.
After running for 1 year, the situation that the iodine simple substance is lost does not occur in the reactor of the facility, and the water outlet effect is stable (the concentration of hypophosphite is less than or equal to 1 mg/L).
Comparative example
The chemical nickel plating waste liquid which is separately collected in a sewage treatment plant in a certain electroplating park is treated by adopting a conventional fixed bed filled active carbon reactor. Wherein the daily treated water amount is 40t, the hypophosphite content is 450-550 mg/L, and the device operation time is 12 h/d. The specific operating conditions are as follows:
firstly, an air-flotation flocculating agent is added into a coagulation air-flotation tank of a pretreatment unit, and the air-flotation flocculating agent and suspended matters in the wastewater form flocs through flocculation; meanwhile, orthophosphate in the wastewater reacts with the air flotation flocculating agent to generate insoluble suspended matters; the insoluble suspended matters and the flocs rise to the water surface under the aeration action of the aeration device to form suspended scum; the floating scum is scraped under the action of the scum scraper, and solid-liquid separation is realized to remove impurities and macromolecular organic matters in the wastewater. Then enters a sand filtration treatment unit to intercept insoluble solid impurities in the waste liquid, and the effluent enters a fixed bed. Two groups of fixed bed reaction groups which run in parallel are arranged in total, each group is connected with 3 reaction tanks in series, and the height of activated carbon filled in the reaction tanks is 2.5m, and the diameter is 1 m.
After the equipment is operated for one month, because the active carbon in the reaction tank is not remixed according to the requirement, the phenomena of reduced oxidation rate and poor water outlet effect begin to occur. After running for half a month, detection of iodide ions in the effluent started. Therefore, the method is modified, namely, all the active carbon in the reaction tank is taken out, mixed and adsorbed again with iodine, and then is filled into the reaction tank. The oxidation rate of the apparatus was restored after adjustment, and the activated carbon in the reaction tank was now remixed every two weeks. The operation is stable for 1 year, and no iodine loss occurs. However, the process of mixing each time is large in engineering quantity and complicated, and certain medicament investment is needed.
Therefore, according to the invention, the air compressor is periodically started, air is introduced into the air pipe through the air inlet pipe by the air compressor, so that a negative pressure state is formed near the air inlet at the bottom end of the air pipe, wastewater and active carbon particles near the air inlet are pumped into the air pipe under pressure difference and ascend to the air outlet at the top end, the wastewater and the active carbon particles are discharged out of the air pipe, and then the wastewater and the active carbon particles fall back to the reaction bed under the action of gravity, so that the active carbon particles losing iodine elementary substances at the lower part of the reaction bed are turned over to the upper part to re-adsorb the iodine elementary substances, and the iodine elementary substances are prevented from being separated from the reaction bed in a water flow migration process to cause loss. The device has the advantages of simple structure, easy maintenance and good application prospect.
The above embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical solutions obtained by means of equivalent substitution or equivalent transformation all fall within the protection scope of the present invention.
Claims (8)
1. A hypophosphite treatment facility for realizing iodine recycling is characterized by comprising a coagulation air flotation unit (1), a sand filtration unit (2), a dosing unit (3) and a reaction unit (4) which are sequentially communicated through a pipeline, wherein the reaction unit (4) is formed by communicating a plurality of hypophosphite treatment reactors for realizing iodine recycling; a plurality of reaction units (4) are arranged and run in parallel; a plurality of the hypophosphite treatment reactors in each reaction unit (4) are operated in series;
the hypophosphite treatment reactor for realizing iodine recycling comprises a shell (41), an upper end enclosure (42), an interception device (43), an interception support plate (45) and a plurality of air pipes (44); the upper end enclosure (42) is fixed at the top of the shell (41), and the upper end enclosure (42) and the shell (41) jointly form a closed reactor with an inner cavity; the bottom of the reactor is provided with a water inlet, and the top of the reactor is provided with a water outlet; the intercepting device (43) is fixed at the upper part of the inner cavity, the intercepting support plate (45) provided with a plurality of holes is fixed at the lower part of the inner cavity, and the intercepting device (43) and the intercepting support plate (45) respectively and completely cover the cross section of the inner cavity at the position; the inner cavity is axially divided into a water inlet area, a reaction area and a water outlet area by an interception device (43) and an interception supporting plate (45); after the waste liquid enters the inner cavity of the reactor, the waste liquid can only enter the water outlet area after being treated by the reaction area from the water inlet area; activated carbon particles for adsorbing iodine simple substances are filled in the middle lower part of the reaction zone to form a reaction bed, and a plurality of vertical air pipes (44) are also arranged in the reaction zone; the top end of the air pipe (44) extends out of the reaction bed and is lower than the interception device (43), a suspension interval is arranged between the bottom end of the air pipe and the interception supporting plate (45), and an air inlet pipe (46) is coaxially sleeved in an air cavity positioned at the bottom of the air pipe (44); one end of the air inlet pipe (46) extends into the air pipe (44) from the air inlet and keeps a distance with the air pipe (44), and the other end of the air inlet pipe is connected with an air compressor (47) which is positioned outside the reactor and used for supplying air; the air compressor (47) can introduce air into the air pipe (44) through the air inlet pipe (46), so that negative pressure is formed near an air inlet at the bottom end of the air pipe (44), waste liquid and activated carbon particles near the air inlet are pumped into the air pipe (44) under the pressure difference, rise to an air outlet at the top end and overflow, and fall back to the reaction bed under the action of gravity;
the dosing unit (3) is a reaction tank for adjusting the pH value of the wastewater and dosing hydrogen peroxide.
2. The facility for hypophosphite treatment with realization of iodine recycling as set forth in claim 1, characterized in that the upper head (42) is detachably fixed on the top of the shell (41), and the interception device (43) is detachably fixed on the upper part of the inner cavity of the reactor.
3. The facility for realizing the recycling of iodine hypophosphite as claimed in claim 1, characterized in that the shell (41) where the reaction zone is located is a cylindrical structure.
4. The facility for hypophosphite treatment to realize iodine recycling as set forth in claim 1, wherein the interception support plate (45) is a perforated plate with a plurality of holes uniformly formed thereon, and one side thereof in contact with the reaction bed is provided with an interception net for preventing leakage of activated carbon particles; the interception device (43) is an interception net.
5. The facility for hypophosphite treatment with iodine recycle as set forth in claim 1, wherein a plurality of said gas tubes (44) are uniformly arranged in said reaction zone.
6. The facility for realizing the hypophosphite treatment with the iodine recycling as claimed in claim 1, wherein the coagulation air flotation unit (1) is a coagulation air flotation tank, and the sand filtration unit (2) is a sand filter tank.
7. A method for removing hypophosphite from chemical nickel plating waste liquid based on the hypophosphite treatment facility as defined in any of claims 1 to 6, is characterized by comprising the following steps:
introducing the chemical nickel plating waste liquid to be treated into a coagulation air flotation unit (1), and forming flocs by the suspended matters in the waste liquid and an air flotation flocculating agent added into the coagulation air flotation unit (1) through flocculation; meanwhile, orthophosphate in the wastewater reacts with the air flotation flocculant to generate insoluble suspended matters; the insoluble suspended matters and the flocs rise to the water surface under the aeration action of an aeration device in the coagulation air flotation unit (1) to form suspended scum; the suspended floating slag is scraped under the action of a slag scraper, so that solid-liquid separation is realized to further remove impurities and macromolecular organic matters in the wastewater;
the waste liquid treated by the coagulation air flotation unit (1) enters a sand filtration unit (2), and insoluble solid impurities in the waste liquid are intercepted and removed from the waste liquid;
the waste liquid treated by the sand filtering unit (2) enters a medicine adding unit (3), the pH value is adjusted to 1.6-1.8, then the waste liquid is mixed with hydrogen peroxide to obtain pretreated waste water, and the pretreated waste water is introduced into a reaction unit (4);
after slowly flowing through a water inlet area of the hypophosphite treatment device, the pretreated wastewater enters a reaction area, hypophosphite in the pretreated wastewater is oxidized into phosphite by iodine simple substances, the iodine simple substances are reduced into iodine ions, the reduced iodine ions are oxidized into the iodine simple substances by hydrogen peroxide, and the iodine simple substances are adsorbed by activated carbon particles again to realize repeated use; the wastewater treated by the reaction zone flows out of the phosphate treatment device from a water outlet through a water outlet zone; then, adding calcium ions or iron ions into phosphite in the wastewater to react with the phosphite to generate precipitate so as to remove the phosphite in the wastewater;
the air compressor (47) is periodically started, air is introduced into the air pipe (44) through the air inlet pipe (46) through the air compressor (47), a negative pressure state is formed near an air inlet at the bottom end of the air pipe (44), waste water and activated carbon particles near the air inlet are pumped into the air inlet pipe (44) under pressure difference and ascend to an air outlet at the top end, the air outlet pipe (44) is exhausted, then the waste water and the activated carbon particles fall back to the reaction bed under the action of gravity, the activated carbon particles with the iodine elementary substances lost at the lower part of the reaction bed are enabled to be overturned to the upper part to re-adsorb the iodine elementary substances, and therefore the iodine elementary substances are prevented from being separated from the reaction bed along with the water flow migration process to cause loss.
8. The removing method according to claim 7, wherein the adding amount of the hydrogen peroxide is 11.5-14 mL/g of hypophosphite calculated by P element, and the mass fraction of the hydrogen peroxide is 30%.
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| JP5642075B2 (en) * | 2008-09-19 | 2014-12-17 | アイオフィーナ ナチュラル ガス， インコーポレイテッド | Iodine recovery system and method |
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| US5792371A (en) * | 1996-08-22 | 1998-08-11 | Iosolutions Incorporated | Method of disinfecting water with iodine species |
| FR2821616A1 (en) * | 2001-03-01 | 2002-09-06 | Pica | ACTIVE CHARCOAL WITH HIGH ADSORPTION CAPACITY AND LOW PHOSPHORIC RESIDUAL CONTENT, PROCESS FOR PREPARING SAME AND APPLICATIONS |
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