CN115677088A - Treatment method of phosphorus removal resin regeneration waste liquid - Google Patents
Treatment method of phosphorus removal resin regeneration waste liquid Download PDFInfo
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- CN115677088A CN115677088A CN202211220287.XA CN202211220287A CN115677088A CN 115677088 A CN115677088 A CN 115677088A CN 202211220287 A CN202211220287 A CN 202211220287A CN 115677088 A CN115677088 A CN 115677088A
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- removal resin
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- 239000011574 phosphorus Substances 0.000 title claims abstract description 150
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 150
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 239000007788 liquid Substances 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 59
- 229920005989 resin Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000008929 regeneration Effects 0.000 title claims abstract description 42
- 238000011069 regeneration method Methods 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007800 oxidant agent Substances 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims description 49
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 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 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 238000010517 secondary reaction Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 230000000694 effects Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for treating phosphorus removal resin regeneration waste liquid, and belongs to the technical field of waste water treatment. The method uses persulfate as an oxidant, at least one of nickel powder, aluminum powder and cobalt powder as a catalyst of an oxidation reaction, and performs oxidation through a two-stage reaction kettle, wherein the temperature of the first-stage oxidation reaction is 85-95 ℃, the temperature of the second-stage oxidation reaction is 60-70 ℃, so that organic phosphorus in the regenerated waste liquid of the phosphorus removal resin can be efficiently converted into positive phosphorus under the non-high-temperature and high-pressure conditions, then the organic phosphorus in the regenerated waste liquid of the phosphorus removal resin is greatly removed through precipitation and filter pressing, and the phosphorus content in the finally discharged sewage is less than or equal to 1.5ppm.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating phosphorus removal resin regeneration waste liquid.
Background
After the industrial wastewater containing organic phosphorus is treated by a coagulation biochemical system, the organic phosphorus in the wastewater hardly reaches the discharge standard, and the methods for treating the organic phosphorus are mostly oxidation and biochemical treatment, and when the water quantity is large and the organic phosphorus content is low, the cost of the oxidation and biochemical treatment is too high.
The prior art reports that the effect of removing organic phosphorus is better by treating phosphorus-containing wastewater through resin adsorption; however, in the generated regenerated waste liquid of the phosphorus removal resin, more organic phosphorus still exists, which is equivalent to that the organic phosphorus is transferred from the industrial wastewater to another waste liquid and is not removed. If the waste liquid is returned to the coagulation process for treatment, the treatment pressure of the biochemical system is increased, and the maintenance of the biochemical system is not facilitated, so that the efficiency is reduced.
The prior art CN106477772A discloses a phosphorus removal and phosphorus resource recovery method for high-phosphorus industrial sewage, which comprises the steps of adding an oxidant (such as persulfate) into the sewage to be treated, stirring and oxidizing to convert organic phosphorus into positive phosphorus and further removing the positive phosphorus. However, persulfate is used as an oxidizing agent, and usually requires high temperature (above 100 ℃) and high pressure to convert organic phosphorus into phosphorus, and the high temperature and high pressure have high requirements on wastewater treatment equipment and high cost. After the method is used for treating sewage, the phosphorus content in the discharged sewage is 3-5 mg/L, namely about 3-5 ppm, the phosphorus content is still high, and the direct discharge standard of sewage cannot be met in the field with strict requirements on the phosphorus content.
Therefore, it is necessary to provide a method for treating a phosphorus removal resin regeneration waste liquid, which can effectively remove organic phosphorus in the waste liquid, so that the phosphorus removal resin regeneration waste liquid containing organic phosphorus reaches the discharge standard, and can still meet the requirements when the water amount is large and the phosphorus content is low.
Disclosure of Invention
The invention aims to overcome the defect of poor dephosphorization effect in the prior art and provide a method for treating the regeneration waste liquid of the dephosphorization resin. The treatment method of the invention uses specific oxidant and catalyst, and carries out oxidation by two-stage reaction kettle, so that organic phosphorus is converted into positive phosphorus under non-high temperature condition, and then the organic phosphorus in the regenerated waste liquid of the phosphorus removal resin is greatly removed by precipitation and filter pressing, and the phosphorus content in the finally discharged sewage is less than or equal to 1.5ppm.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating phosphorus removal resin regeneration waste liquid comprises the following steps:
s1, adjusting the pH value of the phosphorus removal resin regeneration waste liquid to 6-9, and concentrating to obtain pretreated wastewater;
s2, adding the pretreated wastewater into a primary reaction kettle, adding an oxidant and a catalyst, and carrying out oxidation reaction at the temperature of 85-95 ℃ to obtain primary oxidation wastewater;
s3, overflowing the primary oxidation wastewater into a secondary reaction kettle, adding an oxidant, and carrying out an oxidation reaction at a temperature of 60-70 ℃ to obtain secondary oxidation wastewater;
s4, adding the secondary oxidation wastewater into a tertiary reaction kettle, adding a precipitator, performing coagulating sedimentation, and performing filter pressing to discharge filtrate;
wherein in steps S2 and S3, the oxidizing agent is a persulfate; in step S2, the catalyst is at least one of nickel powder, aluminum powder, and cobalt powder.
The method for treating the phosphorus removal resin regeneration waste liquid adopts two-stage oxidation treatment, the oxidation reaction in the step S2 is first-stage oxidation treatment, and the pretreated waste water is subjected to oxidation reaction in a first-stage reaction kettle under the condition that persulfate oxidant and metal powder catalyst exist and under the mild condition of less than 100 ℃; the oxidation reaction in the step S3 is a second-stage oxidation treatment, the wastewater subjected to the first-stage oxidation treatment overflows into a second-stage reaction kettle, and the second-stage oxidation reaction is carried out at a milder temperature in the presence of an oxidant.
When the persulfate is at about 60 ℃, a peroxide bond is broken to generate hydroxyl free radicals, the strong oxidizing property is realized, and the temperature of the oxidation reaction can be reduced to be below 100 ℃ under the catalytic action of metal powder, so that the oxidation reaction at a lower temperature (85-95 ℃) is realized, and most of organic phosphorus is oxidized and converted into the positive phosphorus; after the primary oxidation wastewater overflows to the secondary reaction kettle, adding an oxidant for oxidation reaction, so that the residual unoxidized organic phosphorus can be effectively converted into the positive phosphorus. Through two-stage oxidation treatment, the condition of oxidation reaction is milder, the reaction temperature is lower, high-pressure condition is not needed, the reaction efficiency is effectively improved, organic phosphorus is removed more thoroughly, organic phosphorus in the regenerated waste liquid of the phosphorus removal resin is greatly removed, and the phosphorus content in the finally discharged sewage is less than or equal to 1.5ppm.
Preferably, in step S1, the pH is adjusted by using sulfuric acid or sodium hydroxide according to the pH of the feed water of the phosphorus removal resin regeneration waste liquid.
Preferably, in step S2, the temperature of the oxidation reaction is 89 to 95 ℃.
Preferably, in step S3, the temperature of the oxidation reaction is 63 to 70 ℃.
In the temperature of the oxidation reaction, the organic phosphorus can be efficiently oxidized into the positive phosphorus, and energy waste can not be caused.
In steps S2 and S3, the amounts of the oxidizing agent and the catalyst added are correlated with the phosphorus content in the wastewater.
Preferably, in the step S2, the mass ratio of the oxidant to the catalyst to the phosphorus in the pretreated wastewater is (15-25) to (0.8-1.5) to 1.
Preferably, in the step S3, the mass ratio of the oxidant to the phosphorus in the pretreated wastewater is (4-10): 1.
The addition amounts of the oxidizing agent and the catalyst are related to the phosphorus content in the pretreated wastewater. Generally, the higher the phosphorus content, the greater the amount of oxidant and catalyst added. The inventors have found that, when the oxidizing agent and the catalyst are added in the above-mentioned amounts, organic phosphorus can be completely oxidized into positive phosphorus, and the oxidation efficiency is high.
Because the catalyst can enter the second-stage reaction kettle from the first-stage reaction kettle along with overflow, no catalyst needs to be additionally added in step S3.
Preferably, in the steps S2 and S3, the retention time of the wastewater in the first-stage reaction kettle and the second-stage reaction kettle is 40-50 min.
More preferably, in steps S2 and S3, the retention time of the wastewater in the first-stage reaction kettle and the second-stage reaction kettle is 43-48 min.
Preferably, the overflow water flow rate is 0.2-0.4 m/s.
The inventor researches and discovers that the two-stage oxidation step can basically realize the conversion of organic phosphorus into positive phosphorus when the retention time of the wastewater in the first-stage reaction kettle and the second-stage reaction kettle reaches more than 40 min.
Preferably, the oxidizing agent is at least one of potassium persulfate, sodium persulfate and ammonium persulfate. More preferably, the oxidizing agent is potassium persulfate.
Compared with other persulfates, the potassium persulfate has stronger oxidation effect on the organic phosphorus in the regenerated waste liquid of the phosphorus removal resin and has higher oxidation reaction efficiency.
Preferably, the catalyst is aluminum powder.
The aluminum powder and the potassium persulfate have a certain synergistic effect, and compared with other nickel powder or cobalt powder, the catalytic effect of the aluminum powder on the potassium persulfate is more excellent.
Preferably, the particle size of the catalyst is 0.5 to 100 μm.
Preferably, in step S4, the precipitant is a mixture of polymeric ferric sulfate, polyaluminum and calcium hydroxide.
The addition of the polymeric ferric sulfate can remove the positive phosphorus and ensure the effluent quality, and chloride ions are not introduced to influence the effluent quality like polymeric ferric chloride; the addition of the polyaluminium can remove the orthophosphoric acid and can also precipitate the residual iron ions of the polyferric sulfate; calcium hydroxide removes some of the sulfate while removing the orthophosphoric acid. The addition of the precipitant can remove the phosphorus through coagulating sedimentation.
The polyaluminium is also called polyaluminium chloride, and the content of aluminium oxide in the polyaluminium is one of main factors influencing the performance of the polyaluminium. Preferably, the content of the aluminum oxide in the polyaluminium is more than or equal to 30 percent.
The inventor researches and discovers that the polyaluminium chloride with the content of more than or equal to 30 percent of aluminum oxide has better solubility in the secondary oxidation wastewater, less impurities and high precipitation efficiency.
In step S4, the amount of precipitant added is correlated with the phosphorus content in the wastewater.
Preferably, in the step S4, the mass ratio of the polymeric ferric sulfate, the polymeric aluminum and the calcium hydroxide to the phosphorus in the pretreated wastewater is (3.5-4): (0.35-0.45): 1.
Preferably, the coagulating sedimentation time is 20-30 min.
Preferably, the concentration is a membrane concentration or an evaporative concentration.
When membrane concentration is employed, concentration may be performed using a disk tube reverse osmosis membrane (DTRO membrane). The DTRO membrane can efficiently concentrate the phosphorus removal resin regeneration waste liquid, so that the content of organic phosphorus in the waste liquid reaches more than 10 times of that before being concentrated.
When evaporation concentration is adopted, the subsequent organic phosphorus removal effect is better due to the heating condition, but the evaporation concentration also causes cost rise caused by high temperature, and an evaporator is easy to crystallize and scale.
Through the concentration step, the content of organic phosphorus in the regenerated waste liquid of the phosphorus removal resin is improved, so that the efficiency of treating the waste water is further improved.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for treating a phosphorus removal resin regeneration waste liquid, which uses persulfate as an oxidant and at least one of nickel powder, aluminum powder and cobalt powder as a catalyst, and carries out oxidation through a two-stage reaction kettle, so that organic phosphorus in the phosphorus removal resin regeneration waste liquid can be converted into positive phosphorus under the conditions of non-high temperature and high pressure, then the organic phosphorus in the phosphorus removal resin regeneration waste liquid is greatly removed through precipitation and filter pressing, and finally the phosphorus content in discharged sewage is less than or equal to 1.5ppm.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention, but the examples are not intended to limit the present invention in any way.
The regenerated waste liquid of the dephosphorization resin adopted in the embodiment and the comparative example is taken from the sewage of a dephosphorization waste water section of a certain workshop.
The phosphorus content in the examples of the present invention and the comparative examples was measured according to the following standard method of GBT 11893-1989.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which comprises the following steps:
s1, adjusting the pH =7 of the regenerated phosphorus removal resin waste liquid, filtering to remove large-particle impurities, and concentrating the filtrate by using a DTRO (draw textured reverse osmosis) membrane to obtain pretreated wastewater, wherein the total phosphorus content in the pretreated wastewater is 235ppm;
s2, adding the pretreated wastewater obtained in the step S1 into a primary reaction kettle, adding 4.7g/L of potassium persulfate and 235mg/L of aluminum powder, wherein the mass ratio of potassium persulfate to aluminum powder to phosphorus is 20;
s3, overflowing the primary oxidation wastewater obtained in the step S2 into a secondary reaction kettle at the flow rate of 0.3m/S, adding 1.88g/L of potassium persulfate, namely the mass ratio of potassium persulfate to phosphorus is 8, and carrying out oxidation reaction at 63 ℃ under the stirring condition to obtain secondary oxidation wastewater;
controlling the retention time of the wastewater in the first-stage reaction kettle and the second-stage reaction kettle to be 45min;
s4, pumping the secondary oxidation wastewater obtained in the step S3 into a third-stage reaction kettle, adding 830mg/L polymeric ferric sulfate, 94mg/L polyaluminum and 95mg/L calcium hydroxide, performing coagulative precipitation for 25min, performing filter pressing, and directly discharging filtrate.
Example 2
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2, the addition amount of potassium persulfate is 5.88g/L, and the addition amount of aluminum powder is 352mg/L, namely the mass ratio of potassium persulfate to aluminum powder to phosphorus is 25.5.
Example 3
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2, the addition amount of potassium persulfate is 3.53g/L, and the addition amount of aluminum powder is 188mg/L, namely the mass ratio of potassium persulfate to aluminum powder to phosphorus is 15.8.
Example 4
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2, the addition amount of potassium persulfate is 2.82g/L, and the addition amount of aluminum powder is 164mg/L, namely the mass ratio of potassium persulfate to aluminum powder to phosphorus is 12.
Example 5
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2 and step S3, the mass of potassium persulfate and the like is replaced by ammonium persulfate.
Example 6
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2 and step S3, potassium persulfate and the like is replaced by sodium persulfate.
Example 7
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2, replacing the aluminum powder and other mass with cobalt powder.
Example 8
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S2, the nickel powder is replaced by the aluminum powder in equal mass.
Example 9
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S3, the addition amount of potassium persulfate is 0.94g/L, that is, the mass ratio of potassium persulfate to phosphorus is 4.
Example 10
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in step S3, the addition amount of potassium persulfate is 2.35g/L, namely the mass ratio of potassium persulfate to phosphorus is 10.
Example 11
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in the step S2, the temperature of the oxidation reaction is 95 ℃;
in step S3, the temperature of the oxidation reaction was 70 ℃.
Example 12
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in the step S2, the temperature of the oxidation reaction is 85 ℃;
in step S3, the temperature of the oxidation reaction is 60 ℃.
Example 13
The embodiment provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the embodiment 1 in that:
in the step S1, adjusting the pH =9 of the regenerated waste liquid of the phosphorus removal resin, and concentrating in an evaporation and concentration mode;
in step S3, the overflow rate is 0.4m/S; controlling the retention time of the wastewater in the first-stage reaction kettle and the second-stage reaction kettle to be 40min;
in the step S4, 940mg/L polymeric ferric sulfate, 105mg/L polyaluminium and 83mg/L calcium hydroxide are added, and the coagulating sedimentation time is 30min.
Comparative example 1
The comparative example provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the method in example 1 in that:
no catalyst was added in step S2.
Comparative example 2
The comparative example provides a method for treating phosphorus removal resin regeneration waste liquid, and the method is different from the method in example 1 in that:
in step S2, the aluminum powder and other mass is replaced by iron powder.
Comparative example 3
The comparative example provides a method for treating a phosphorus removal resin regeneration waste liquid, which is different from the method in example 1 in that:
in step S2, the temperature of the oxidation reaction was 80 ℃.
Comparative example 4
The comparative example provides a method for treating phosphorus removal resin regeneration waste liquid, and the method is different from the method in example 1 in that:
in step S3, the temperature of the oxidation reaction is 50 ℃.
Comparative example 5
The comparative example provides a method for treating a phosphorus removal resin regeneration waste liquid, which comprises the following steps:
s1, adjusting the pH =7 of the regenerated phosphorus removal resin waste liquid, filtering to remove large-particle impurities, and concentrating the filtrate by using a DTRO (draw textured reverse osmosis) membrane to obtain pretreated wastewater, wherein the total phosphorus content in the pretreated wastewater is 235ppm;
s2, adding the pretreated wastewater obtained in the step S1 into a primary reaction kettle, adding 6.58g/L of potassium persulfate and 235mg/L of aluminum powder, wherein the mass ratio of the potassium persulfate to the aluminum powder to the phosphorus is 28;
controlling the retention time of the wastewater in the first-stage reaction kettle to be 45min;
s3, directly pumping the first-stage oxidation wastewater obtained in the step S1 into a third-stage reaction kettle, adding 830mg/L polymeric ferric sulfate, 94mg/L polyaluminum and 95mg/L calcium hydroxide, performing coagulative precipitation for 25min, performing filter pressing, and directly discharging filtrate.
Comparative example 6
The comparative example provides a method for treating phosphorus removal resin regeneration waste liquid, and the method is different from the comparative example 5 in that:
in the step S2, the temperature of the oxidation reaction is 63 ℃; the retention time of the wastewater in the first-stage reaction kettle is controlled to be 60min.
Performance test
The phosphorus content of the filtrate discharged last in the examples and comparative examples was measured, and the results are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Phosphorus content (ppm) | Not detected out | 0.1 | 0.1 | 1.4 | 0.2 | 0.1 | 0.2 |
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | ||
| Phosphorus content (ppm) | 0.1 | 0.1 | 0.1 | 0.1 | 1.3 | 0.2 | |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | ||
| Phosphorus content (ppm) | 59.5 | 42.1 | 8.5 | 5.7 | 3.1 | 22.4 |
According to the test results in Table 1, it can be seen that the phosphorus content in the finally discharged sewage is less than or equal to 1.5ppm by treating the regenerated waste liquid of the phosphorus removal resin according to the method of the present invention, such that the organic phosphorus in the regenerated waste liquid of the phosphorus removal resin is greatly removed.
According to the test results of the examples 1 to 4, the phosphorus content in the wastewater discharged in the examples 1 to 3 is relatively lower, which shows that the phosphorus removal effect is better when the mass ratio of the oxidant, the catalyst and the phosphorus in the pretreated wastewater is (15-25): (0.8-1.5): 1 in the step S2.
According to the embodiments 1 and 5 to 8, it can be seen that, when the oxidizing agent is potassium persulfate and the catalyst is aluminum powder, the oxidizing effect on the organic phosphorus is better, and more organic phosphorus is converted into the positive phosphorus and removed.
According to example 1, example 11 and example 12, it can be seen that when the temperature of the oxidation reaction is low in step S2 and step S3, the oxidation efficiency is slow, and the oxidation effect of organic phosphorus is relatively poor. Therefore, the temperature of the oxidation reaction in step S2 is preferably 89 to 95 ℃ and the temperature of the oxidation reaction in step S3 is preferably 63 to 70 ℃.
In comparative example 1, which contains no catalyst and only potassium persulfate as an oxidizing agent, organic phosphorus is difficult to be oxidized to positive phosphorus at 100 ℃ or lower, and the phosphorus content in the final effluent is too high, and phosphorus is not effectively removed. In comparative example 2, iron powder is used as a catalyst, and the catalytic effect is far inferior to that of nickel powder, aluminum powder and cobalt powder adopted by the invention. According to comparative examples 3 and 4, when the temperature of the oxidation reaction is too low, the conversion efficiency of organic phosphorus is low, and the phosphorus removal effect is poor. According to comparative examples 5 and 6, when a single-stage oxidation reaction is employed, it is difficult to achieve the high phosphorus removal effect obtained in the examples of the present application even if the oxidation reaction time is prolonged accordingly.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for treating a phosphorus removal resin regeneration waste liquid is characterized by comprising the following steps:
s1, adjusting the pH value of the phosphorus removal resin regeneration waste liquid to 6-9, and concentrating to obtain pretreated wastewater;
s2, adding the pretreated wastewater into a primary reaction kettle, adding an oxidant and a catalyst, and carrying out oxidation reaction at the temperature of 85-95 ℃ to obtain primary oxidation wastewater;
s3, overflowing the primary oxidation wastewater into a secondary reaction kettle, adding an oxidant, and carrying out an oxidation reaction at the temperature of 60-70 ℃ to obtain secondary oxidation wastewater;
s4, adding the secondary oxidation wastewater into a tertiary reaction kettle, adding a precipitator, performing coagulating sedimentation, and performing filter pressing to discharge filtrate;
wherein in steps S2 and S3, the oxidizing agent is a persulfate; in step S2, the catalyst is at least one of nickel powder, aluminum powder, and cobalt powder.
2. The method for treating the regenerated phosphorus-removing resin waste liquid as claimed in claim 1, wherein in step S2, an oxidant and a catalyst are added according to the content of phosphorus in the pretreated wastewater, and the mass ratio of the oxidant to the catalyst to the phosphorus in the pretreated wastewater is (15-25) to (0.8-1.5) to 1.
3. The method for treating the phosphorus removal resin regeneration waste liquid as claimed in claim 1, wherein in step S3, an oxidant is added according to the content of phosphorus in the pretreated waste water, and the mass ratio of the oxidant to the phosphorus in the pretreated waste water is (4-10) to 1.
4. The method for treating the phosphorus removal resin regeneration waste liquid according to claim 1, wherein the oxidant is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
5. The method for treating the phosphorus removal resin regeneration waste liquid as claimed in claim 1, wherein the oxidizing agent is potassium persulfate, and the catalyst is aluminum powder.
6. The method for treating the regenerated waste liquid of phosphorus removing resin as claimed in claim 1, wherein in step S3, the flow rate of the overflow water is 0.2-0.4 m/S.
7. The method for treating phosphorus removal resin regeneration waste liquid as claimed in claim 1, wherein in step S4, the precipitant is a mixture of polymeric ferric sulfate, polyaluminum and calcium hydroxide.
8. The method for treating the phosphorus removal resin regeneration waste liquid as claimed in claim 1, wherein in the step S4, the coagulating sedimentation time is 20-30 min.
9. The method for treating the phosphorus removal resin regeneration waste liquid as claimed in claim 1, wherein in step S1, the concentration is membrane concentration or evaporation concentration.
10. The method for treating the regenerated waste liquid of phosphorus removal resin as claimed in claim 9, wherein the membrane concentration is performed by using a disk-tube reverse osmosis membrane.
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| PCT/CN2023/077164 WO2024074004A1 (en) | 2022-10-08 | 2023-02-20 | Phosphate removal resin regenerated waste liquid treatment method |
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| JPH09141274A (en) * | 1995-11-15 | 1997-06-03 | Kankyo Eng Kk | High-degree treatment for waste water containing phosphorus |
| JP2002361269A (en) * | 2001-06-06 | 2002-12-17 | Nippon Gosei Alcohol Kk | Method for treating water containing phosphorus |
| CN102020350A (en) * | 2011-01-04 | 2011-04-20 | 华中师范大学 | Processing method of heterocatalysis persulfate Fenton oxidation water |
| CN103058346B (en) * | 2011-10-18 | 2014-12-03 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN107555649B (en) * | 2017-08-09 | 2021-06-01 | 北京高能时代环境技术股份有限公司 | Method for deeply removing organic phosphorus in wastewater |
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