CN115819782B - Liquid resin, preparation method and application thereof in copper-containing wastewater treatment - Google Patents
Liquid resin, preparation method and application thereof in copper-containing wastewater treatment Download PDFInfo
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- CN115819782B CN115819782B CN202211555585.4A CN202211555585A CN115819782B CN 115819782 B CN115819782 B CN 115819782B CN 202211555585 A CN202211555585 A CN 202211555585A CN 115819782 B CN115819782 B CN 115819782B
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- 239000007788 liquid Substances 0.000 title claims abstract description 467
- 239000011347 resin Substances 0.000 title claims abstract description 429
- 229920005989 resin Polymers 0.000 title claims abstract description 429
- 238000002360 preparation method Methods 0.000 title claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 97
- 229910052802 copper Inorganic materials 0.000 title abstract description 96
- 239000010949 copper Substances 0.000 title abstract description 96
- 238000004065 wastewater treatment Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 claims abstract description 28
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 claims abstract description 24
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 20
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 20
- UHSURKDCQCGNGM-UHFFFAOYSA-N 5-(2-hydroxyimino-2-phenylethyl)nonan-2-ol Chemical compound CCCCC(CCC(C)O)CC(=NO)C1=CC=CC=C1 UHSURKDCQCGNGM-UHFFFAOYSA-N 0.000 claims abstract description 19
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims abstract description 17
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 abstract description 64
- 230000008929 regeneration Effects 0.000 abstract description 57
- 238000001179 sorption measurement Methods 0.000 abstract description 45
- 239000002351 wastewater Substances 0.000 abstract description 40
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 36
- 229910001431 copper ion Inorganic materials 0.000 abstract description 36
- 230000008569 process Effects 0.000 abstract description 29
- 229920006395 saturated elastomer Polymers 0.000 abstract description 25
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 239000013522 chelant Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 239000002699 waste material Substances 0.000 description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 238000005530 etching Methods 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- -1 diethylenetriamine penta methylene phosphonic acids Chemical class 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000012492 regenerant Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- TUIVYNSSLYLUQW-UHFFFAOYSA-N 2-ethylhexylphosphinic acid Chemical compound CCCCC(CC)CP(O)=O TUIVYNSSLYLUQW-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 125000003544 oxime group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- MJUVQSGLWOGIOB-UHFFFAOYSA-N 2-[(Z)-hydroxyiminomethyl]-4-nonylphenol Chemical compound OC1=C(C=N/O)C=C(C=C1)CCCCCCCCC MJUVQSGLWOGIOB-UHFFFAOYSA-N 0.000 description 1
- IMLWJBZEFFYHCR-UHFFFAOYSA-N 4-dodecyl-2-hydroxybenzaldehyde Chemical compound CCCCCCCCCCCCC1=CC=C(C=O)C(O)=C1 IMLWJBZEFFYHCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses liquid resin which comprises the following components in parts by weight: 1 to 2 parts of diethylenetriamine pentamethylene phosphonic acid, 0.5 to 2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1 to 2 parts of salicylaldoxime, 0.1 to 0.2 part of 2, 6-di-tert-butylhydroquinone and 10 to 20 parts of organic solvent. The liquid resin can generate metal chelate with copper ions in a strong acid (pH < 1), strong complexing and strong oxidizing water environment, so that the copper ions are efficiently grasped out and enriched in the liquid resin, and the service life of the liquid resin is effectively prolonged; the method for regenerating the liquid resin comprises the steps of carrying out regeneration by using nonylphenol and concentrated sulfuric acid after the liquid resin is adsorbed and saturated, wherein the regeneration rate of the liquid resin is up to more than 95%, and the liquid resin is subjected to adsorption grabbing of copper ions in the next round after regeneration; when the liquid resin is used for treating copper-containing wastewater in the electronic industry, continuous production in the treatment process is realized by arranging three liquid resin towers which are connected end to end, and two liquid resin towers in the three liquid resin towers in the operation process are operated in series, and one regeneration is realized.
Description
Technical Field
The invention relates to a liquid resin, a preparation method of the liquid resin and application of the liquid resin in copper-containing wastewater treatment.
Background
Copper-containing wastewater produced in electronic industries such as semiconductors, panels, electroplating and the like contains a large amount of copper ions and substances such as complex copper, hydrogen peroxide, hydrofluoric acid and the like, has the characteristics of strong acidity (pH is less than 1), strong oxidizing property, strong complexing property and the like, and has the problems of high treatment difficulty, high treatment cost and the like compared with the ionic copper-containing wastewater treatment in industries such as mines, smelting, chemical industry, hardware and the like, the existing method for treating the complex water quality mainly comprises a chemical coagulating sedimentation method, copper in the wastewater is separated from the water in a chelate precipitation mode by adding a large amount of liquid alkali, recapturing agents, coagulating flocculants and the like, the generated copper-containing sludge is dangerous waste sludge, the generated copper ion is required to be treated outside the user at a higher price, and the effluent is often not up to standard due to water quality fluctuation.
Copper is used as a widely used metal, and is used for treating real resource waste in a precipitation mode. The research of the existing method focuses on treating copper-containing wastewater and realizing further resource utilization after copper is captured. As in patent CN 103952551A, 2-hydroxy-5-nonylbenzaldoxime, 2-hydroxy-5-nonylacetophenone oxime, 4-dodecyl-2-hydroxybenzaldehyde, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and kerosene are used as main formulas to adsorb copper-containing wastewater, and the adsorption rate reaches 98%, but the method is only suitable for adsorbing copper-containing wastewater with pH of 2-8, and can not treat strong acid wastewater with pH less than 1, and has limitations.
Disclosure of Invention
The invention aims to: one of the purposes of the present invention is to provide a liquid resin which can still have a high adsorption rate to copper ions in a strongly acidic (pH < 1), strongly complexing and strongly oxidizing aqueous environment, and another purpose of the present invention is to provide a method for preparing the liquid resin.
The technical scheme is as follows: the liquid resin provided by the invention comprises the following components in parts by weight: 1 to 2 parts of diethylenetriamine pentamethylene phosphonic acid, 0.5 to 2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1 to 2 parts of salicylaldoxime, 0.1 to 0.2 part of 2, 6-di-tert-butylhydroquinone and 10 to 20 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) The preparation method comprises the steps of (1) stirring and mixing a formula amount of diethylenetriamine penta (methylene phosphonic acid) and 2-hydroxy-5-nonylacetophenone oxime at normal temperature to obtain a mixture; 2-hydroxy-5-nonylacetophenone oxime has excellent phase separation property, and improves the separation speed of liquid resin and copper-containing wastewater after adsorption;
(2) Adding a formula amount of salicylaldoxime into the mixture in the step (1), and reacting at a high temperature to obtain a product I with a net structure;
(3) Taking 2, 6-di-tert-butylhydroquinone (2, 6-di-tert-butylhydroquinone is solid and needs to be heated and dissolved), heating and dissolving, then adding into a product I for dehydration reaction, and obtaining a product II after the reaction;
(4) Mixing the product II with a formula amount of organic solvent to obtain liquid resin. The liquid resin and the liquid copper wastewater are subjected to reaction, and compared with the solid resin and the liquid copper wastewater, the liquid resin and the copper wastewater have larger contact area and higher copper grasping efficiency; in addition, the product II is in a liquid viscous state, has poor fluidity and poor separation effect, so that the product II is dissolved by an organic solvent and then reacts with copper wastewater.
Under the high temperature condition, phosphorus-oxygen double bond of diethylenetriamine penta methylene phosphonic acid and hydroxyl in a hydroxyl imine structure C=N-OH of salicylaldoxime are rapidly reacted to form hydrogen bonds, under the action of the hydrogen bonds, a plurality of diethylenetriamine penta methylene phosphonic acids are connected with a plurality of salicylaldoxime to form a product I with large molecular weight and a netlike three-dimensional structure, lone pair electrons on hydroxyl oxygen and oximido nitrogen of the product I coordinate with copper ions in wastewater, the adsorptivity and stability of the product I with large molecular weight and netlike three-dimensional structure to the copper ions (the stability means that adsorbed copper is not easy to desorb, and the copper is stably adsorbed on resin) are greatly enhanced, so that copper ions can be stably grasped under the condition that the hydrogen ion content is more (the pH is less than 1), and copper ions can be grasped from complex copper;
the salicylaldoxime has a hydroxyl imine structure C=N-OH (the hydroxyl imine structure is represented by RH), has a carbon-nitrogen double bond, has a lower valence of N atoms, and is easy to undergo free radical oxidation reaction, wherein the oxidation reaction is as follows:
RH+H 2 O 2 →R - +HOO - +H 2 O
R - +H 2 O 2 →ROO - +H 2 O
ROO - +RH→HOO - +2R -
oxidative decomposition of the hydroxyimine structure to reactive radicals (R) - ) The free radical can react with hydrogen peroxide to generate new free Radical (ROO) - ) The repeated circulation makes the oxidation reaction proceed according to the free radical chain process, which causes the salicylaldoxime to oxidize and destroy the net-shaped three-dimensional structure of the product I, thereby reducing the adsorptivity and stability to copper ions. The benzene ring of the 2, 6-di-tert-butylhydroquinone has alkyl dispersed electrons to play a role of stabilizing free radicals, and can react with chain growth free radicals (R - Or ROO (r) - ) The reaction is carried out, so that the chain reaction is interrupted, and the antioxidation effect is achieved;
2, 6-di-tert-butylhydroquinone is loaded on the product I, so that chain reaction is reduced, oxidation resistance of the final product liquid resin is improved, adsorption efficiency of the resin is guaranteed, service life of the liquid resin is prolonged, and high adsorptivity of the product I to copper ions is maintained;
the reticular three-dimensional structure formed by diethylenetriamine penta methylene phosphonic acid and salicylaldoxime has strong chelating property for copper ions, can stably adsorb copper ions under the water quality condition that the pH value is less than 1, and has high adsorption rate for complex copper; the benzene ring of the 2, 6-di-tert-butylhydroquinone has the effect of stabilizing free radicals by alkyl dispersed electrons, so that the chain reaction is reduced, the oxidation resistance of the final product liquid resin is improved, the adsorption efficiency of the liquid resin is ensured, and the service life of the liquid resin is prolonged.
Wherein, in the step (2), the reaction temperature is not lower than 60 ℃; the effect of the high temperature is to reduce the reaction activation energy and promote the combination of the phosphorus-oxygen double bond and the hydroxyl group in the hydroxyl imine structure C=N-OH.
Wherein, in the step (3), the heating temperature is 35-40 ℃.
The regeneration method of the liquid resin specifically comprises the following steps: washing liquid resin for treating copper-containing wastewater in the electronic industry, adding nonylphenol and sulfuric acid with the mass fraction not lower than 15% into the liquid resin, and treating for 5-8 min (each liquid resin tower regenerates for 5-8 min) to obtain regenerated liquid resin.
Wherein the addition amount of the nonylphenol is 0.2 to 0.5 times of the mass of the liquid resin; the adding volume of the sulfuric acid is 1/2-1/5 of the volume of the liquid resin.
The nonylphenol can form stronger hydrogen bonds with hydroxyl and oxime groups under the action of concentrated sulfuric acid serving as a catalyst, the chelating capacity of the hydroxyl, oxime groups and copper ions is weakened, the copper ions are replaced by the hydrogen ions, the regeneration efficiency of the liquid resin is improved, and the regeneration rate of the liquid resin is up to more than 95%.
The application of the liquid resin in treating copper-containing wastewater in the electronic industry.
Wherein, the reactor adopted in the application process is as follows: the device comprises three liquid resin towers which are connected end to end; each liquid resin tower comprises a waste liquid inlet, a waste liquid outlet, a regenerant inlet and a regenerant outlet; the waste liquid inlets of the three liquid resin towers are respectively connected with a waste liquid tank through liquid inlet pipelines, and the liquid inlet pipelines are provided with electric control valves I; the liquid waste outlets of the three liquid resin towers are connected with a liquid outlet pipeline, the liquid outlet pipeline is divided into a first liquid outlet pipeline and a second liquid outlet pipeline, the liquid resin tower of the upper stage is connected with the liquid waste inlet of the liquid resin tower of the next stage through the first liquid outlet pipeline, and the second liquid outlet pipeline of the liquid resin tower is connected with a subsequent water treatment unit; the first liquid outlet pipeline and the second liquid outlet pipeline are respectively provided with an electric control valve II and a copper ion concentration detector; the regenerated liquid outlets of the three liquid resin towers are connected with an external recycling treatment unit through a liquid discharge pipeline, and an electric control valve III is arranged on the liquid discharge pipeline; the regenerant inlets of the three liquid resin towers are connected with the regenerant tank through a connecting pipeline, and an electric control valve IV is arranged on the connecting pipeline.
Wherein baffles used for increasing the reaction time of the liquid resin and the copper-containing wastewater are arranged in the three liquid resin towers.
The specific operation process of the reactor is as follows: when two liquid resin towers are operated in series for at least 18 hours, an electric control valve on a liquid inlet pipeline of a previous stage liquid resin tower and a waste liquid tank and an electric control valve on a first liquid outlet pipeline of the previous stage liquid resin tower are closed, and simultaneously, an electric control valve on a connecting pipeline of the stage liquid resin tower and a regenerant tank and an electric control valve on a liquid discharge pipeline of the stage liquid resin tower are started; starting an electric control valve on a liquid inlet pipeline of the liquid resin tower at the next stage and the waste liquid tank and starting an electric control valve on a second liquid outlet pipeline of the liquid resin tower at the next stage, and switching the liquid outlet pipeline of the liquid resin tower at the next stage to be connected with a waste liquid inlet of the liquid resin tower at the next stage; the reactor was continuously operated in the above manner was repeated.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The liquid resin can generate metal chelate with copper ions in a strong acid (pH < 1), strong complexing and strong oxidizing water environment, so that the copper ions are efficiently grasped out and enriched in the liquid resin, and the service life of the liquid resin is effectively prolonged; (2) The method for regenerating the liquid resin by using the nonylphenol and the concentrated sulfuric acid after the liquid resin is adsorbed and saturated has the regeneration rate of more than 95 percent, and the liquid resin is subjected to the next round of copper ion adsorption and grabbing after the regeneration, so that the service life of the liquid resin is effectively prolonged; (3) When the liquid resin is used for treating copper-containing wastewater in the electronic industry, continuous production is realized by arranging three liquid resin towers which are connected end to end and running two liquid resin towers in the three liquid resin towers in series in the running process, and the liquid resin has high capability of capturing copper ions and good regeneration effect, so that the (copper sulfate) in the regenerated liquid has high purity and can be recycled, copper sulfate crystals are formed by evaporation and crystallization, or copper simple substances are recovered by an electrolysis mode.
Drawings
FIG. 1 is a flow chart of a reactor operating process.
Detailed Description
Example 1
The liquid resin consists of the following components in parts by weight: 1.5 parts of diethylenetriamine pentamethylene phosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 1 part of salicylaldoxime, 0.15 part of 2, 6-di-tert-butylhydroquinone and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Mixing and stirring the formula amount of diethylenetriamine penta-methylene phosphonic acid and 2-hydroxy-5-nonylacetophenone oxime for 20-30 min at normal temperature to obtain a mixture;
(2) Adding the salicylaldoxime with the formula amount into the mixture in the step (1), and stirring for 20-30 min at 60 ℃ to obtain a product I with a net structure;
(3) Taking 2, 6-di-tert-butylhydroquinone with the formula amount, heating and dissolving the 2, 6-di-tert-butylhydroquinone at the temperature of between 35 and 40 ℃, then adding the 2, 6-di-tert-butylhydroquinone into the product I for dehydration reaction, and rapidly stirring the mixture for 5 to 10 minutes to obtain a product II;
(4) Mixing the product II with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Comparative example 1
The liquid resin consists of the following components in parts by weight: 1.5 parts of diethylenetriamine pentamethylene phosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 0.15 part of 2, 6-di-tert-butylhydroquinone and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Mixing and stirring the formula amount of diethylenetriamine penta-methylene phosphonic acid and 2-hydroxy-5-nonylacetophenone oxime for 20-30 min at normal temperature to obtain a mixture;
(2) Heating and dissolving 2, 6-di-tert-butylhydroquinone with the formula amount at 35-40 ℃, adding the mixture into the mixture, and rapidly stirring the mixture for 5-10 min to obtain a product II;
(3) Mixing the product II with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Comparative example 2
The liquid resin consists of the following components in parts by weight: 1.5 parts of diethylenetriamine pentamethylene phosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 1 part of salicylaldoxime and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Mixing and stirring the formula amount of diethylenetriamine penta-methylene phosphonic acid and 2-hydroxy-5-nonylacetophenone oxime for 20-30 min at normal temperature to obtain a mixture;
(2) Adding the salicylaldoxime with the formula amount into the mixture in the step (1), and stirring for 20-30 min at 60 ℃ to obtain a product I with a net structure;
(3) Mixing the product I with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Comparative example 3
The liquid resin consists of the following components in parts by weight: 1.5 parts of diethylenetriamine pentamethylene phosphonic acid, 1 part of salicylaldoxime, 0.15 part of 2, 6-di-tert-butylhydroquinone and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Adding the salicylaldoxime with the formula amount into the diethylene triamine pentamethylene phosphonic acid with the formula amount, and stirring for 20-30 min at 60 ℃ to obtain a product I with a net structure;
(2) Taking 2, 6-di-tert-butylhydroquinone with the formula amount, heating and dissolving the 2, 6-di-tert-butylhydroquinone at the temperature of between 35 and 40 ℃, then adding the 2, 6-di-tert-butylhydroquinone into the product I for dehydration reaction, and rapidly stirring the mixture for 5 to 10 minutes to obtain a product II;
(3) Mixing the product II with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Comparative example 4
The liquid resin consists of the following components in parts by weight: 0.5 part of diethylenetriamine pentamethylene phosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 2.5 parts of salicylaldoxime, 0.15 part of 2, 6-di-tert-butylhydroquinone and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Mixing and stirring the formula amount of diethylenetriamine penta-methylene phosphonic acid and 2-hydroxy-5-nonylacetophenone oxime for 20-30 min at normal temperature to obtain a mixture;
(2) Adding the salicylaldoxime with the formula amount into the mixture in the step (1), and stirring for 20-30 min at 60 ℃ to obtain a product I;
(3) Taking 2, 6-di-tert-butylhydroquinone with the formula amount, heating and dissolving the 2, 6-di-tert-butylhydroquinone at the temperature of between 35 and 40 ℃, then adding the 2, 6-di-tert-butylhydroquinone into the product I for dehydration reaction, and rapidly stirring the mixture for 5 to 10 minutes to obtain a product II;
(4) Mixing the product II with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Comparative example 5
The liquid resin consists of the following components in parts by weight: 1.5 parts of 2-ethylhexyl phosphinic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 1 part of salicylaldoxime, 0.15 part of 2, 6-di-tert-butylhydroquinone and 15 parts of organic solvent.
The preparation method of the liquid resin comprises the following steps:
(1) Mixing and stirring 2-ethylhexyl phosphinic acid and 2-hydroxy-5-nonylacetophenone oxime in a formula amount for 20-30 min at normal temperature to obtain a mixture;
(2) Adding the salicylaldoxime with the formula amount into the mixture in the step (1), and stirring for 20-30 min at 60 ℃ to obtain a product I;
(3) Taking 2, 6-di-tert-butylhydroquinone with the formula amount, heating and dissolving the 2, 6-di-tert-butylhydroquinone at the temperature of between 35 and 40 ℃, then adding the 2, 6-di-tert-butylhydroquinone into the product I for dehydration reaction, and rapidly stirring the mixture for 5 to 10 minutes to obtain a product II;
(4) Mixing the product II with the organic solvent in the formula amount, and stirring for 30min at normal temperature to obtain the liquid resin.
Example 2
The liquid resin obtained in example 1 was used for treating copper etching waste liquid (the water content in the copper etching waste liquid was 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is filled with water, the liquid resin tower B is discharged, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the discharged water of the liquid resin tower B is detected to be 20-30 mg/L, the copper ion concentration is detected to be 20-30 mg/LWhen the liquid resin tower A enters a regeneration process, the liquid resin tower B and the liquid resin tower C are connected in series to start adsorption operation, the liquid resin tower B is filled with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the effluent of the liquid resin tower C is detected to be 20-30 mg/L, the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is fed with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the effluent of the liquid resin tower A is detected to be 20-30 mg/L, the liquid resin tower C enters a regeneration procedure, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode repeatedly; the copper concentration of the system effluent can reach 20-30 mg/L after the resin towers A, B, B, C, C and A respectively run for 18 hours; the saturated adsorption quantity of the liquid resin is more than 99 percent; and discharging the regenerated liquid obtained by the liquid resin tower A, the liquid resin tower B and the liquid resin tower C into a subsequent electrolysis system to generate high-purity copper simple substance, wherein the purity of copper is 99.99%, and the recovery rate of copper is 99.97%.
Before the liquid resin tower regeneration process, pure water is used for cleaning the liquid resin, a large amount of COD adhered to the liquid resin is washed, the pure water cleaning flow rate is 15BV/h, the pure water amount is 1BV, then nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin) are used for carrying out liquid resin regeneration, the regeneration time is 7.5min, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Example 3
The liquid resin obtained in example 1 was used for treating copper etching waste liquid (the water content in the copper etching waste liquid was 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is fed with water, the liquid resin tower B is discharged, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the discharged water of the liquid resin tower B is detected to be 20-30 mg/L, the liquid resin tower A enters a regeneration process, the liquid resin tower B and the liquid resin tower C are connected in series for starting adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the effluent of the liquid resin tower C is detected to be 20-30 mg/L, the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is fed with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the concentration of copper ions in the effluent of the liquid resin tower A is detected to be 20-30 mg/L, the liquid resin tower C enters a regeneration procedure, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode repeatedly; the copper concentration of the system effluent can reach 20-30 mg/L after the resin towers A, B, B, C, C and A respectively run for 18 hours; the saturated adsorption quantity of the liquid resin is more than 99 percent; and discharging the regenerated liquid obtained by the liquid resin tower A, the liquid resin tower B and the liquid resin tower C into a subsequent electrolysis system to generate high-purity copper simple substance, wherein the purity of copper is 99.99%, and the recovery rate of copper is 99.97%.
The method comprises the steps of firstly cleaning liquid resin by using pure water before a liquid resin tower regeneration process, cleaning a large amount of COD adhered to the liquid resin, wherein the cleaning flow rate of the pure water is 15BV/h, the water quantity of the pure water is 1BV, then regenerating the liquid resin by using sulfuric acid with the mass fraction of 20% (the added volume of the sulfuric acid is 1/3 of the volume of the liquid resin), the regeneration time is 7.5min, the regeneration rate of the liquid resin is 87%, and the residual 12-13% of copper still remains in the liquid resin; the flow rate of the regenerant is 8BV/h, and the drug dosage is 1BV. The reason for the reduction in regeneration efficiency is that nonylphenol is not introduced into the regenerant, so that the regeneration efficiency is reduced.
Example 4
The liquid resin obtained in comparative example 1 was used for treating copper etching waste liquid (copper etching waste liquid, water amount 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is fed with water, the liquid resin tower B is discharged with water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower A enters a regeneration procedure, the liquid resin tower B and the liquid resin tower C are connected in series for starting adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is filled with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower C enters a regeneration process, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode; a+ B, B + C, C +The copper concentration of the system effluent after the resin towers are respectively operated for 18 hours is 1260mg/L; wherein the complexing copper is 600mg/L; and discharging the regenerated liquid obtained by the liquid resin tower A, the liquid resin tower B and the liquid resin tower C into a subsequent electrolysis system to generate high-purity copper simple substance, wherein the purity of copper is 99.95%, and the recovery rate of copper is 99.2%.
The liquid resin is washed by pure water before the liquid resin tower regeneration process, a large amount of COD adhered to the liquid resin is washed, the pure water washing flow rate is 15BV/h, the pure water amount is 1BV, then the liquid resin is regenerated by nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin), the regeneration time is 7.5min, the regeneration rate of the liquid resin is 95%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Example 5
The liquid resin obtained in comparative example 2 was used for treating copper etching waste liquid (the water content in the copper etching waste liquid was 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is fed with water, the liquid resin tower B is discharged with water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower A enters a regeneration procedure, the liquid resin tower B and the liquid resin tower C are connected in series for starting adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; when the liquid resin tower B is in liquid stateAfter the resin is fully adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is filled with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower C enters a regeneration process, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode;
table 1 shows the copper adsorption efficiency after the liquid resin of comparative example 2 was run for 1 to 6 cycles (18 hours per cycle) and the copper ion concentration in the system effluent
As shown in table 1, as the operation cycle proceeds, the adsorption efficiency of the liquid resin gradually decreases, and the copper concentration of the system effluent is higher and higher, because the 2, 6-di-tert-butylhydroquinone antioxidant is not introduced into the liquid resin, so that the liquid resin is oxidized by hydrogen peroxide, resulting in gradual decrease of the adsorption efficiency.
The liquid resin is washed by pure water before the liquid resin tower regeneration process, a large amount of COD adhered to the liquid resin is washed, the pure water washing flow rate is 15BV/h, the pure water amount is 1BV, then the liquid resin is regenerated by nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin), the regeneration time is 7.5min, the regeneration rate of the liquid resin is 95.8%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Example 6
The liquid resin obtained in comparative example 3 was used for treating copper etching waste liquid (the water content in the copper etching waste liquid was 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is fed with water, the liquid resin tower B is discharged with water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower A enters a regeneration procedure, the liquid resin tower B and the liquid resin tower C are connected in series for starting adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is filled with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower C enters a regeneration process, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode; the copper concentration of the system effluent is 2500mg/L after the A+ B, B + C, C +A resin towers respectively run for 18 hours, and the reason is that the separation speed is reduced after the liquid resin reacts with the copper-containing wastewater due to the lack of 2-hydroxy-5-nonylacetophenone oxime in the liquid resin, so that part of the liquid resin can be discharged along with the effluent, the liquid resin amount in the resin towers is gradually reduced, the copper adsorption rate of the copper-containing wastewater is gradually reduced, and the copper concentration of the system effluent is gradually increased.
Before the liquid resin tower regeneration process, pure water is used for cleaning the liquid resin, a large amount of COD adhered to the liquid resin is washed, the pure water cleaning flow rate is 15BV/h, the pure water amount is 1BV, then nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin) are used for carrying out liquid resin regeneration, the regeneration time is 7.5min, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Example 7
The liquid resin obtained in comparative example 4 was used for treating copper etching waste liquid (copper etching waste liquid, water amount 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is fed with water, the liquid resin tower B is discharged with water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower A enters a regeneration procedure, the liquid resin tower B and the liquid resin tower C are connected in series for starting adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is filled with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower C enters a regeneration process, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode; the copper concentration of the system effluent after each resin tower A+ B, B + C, C +A runs for 18 hours is 855mg/L, wherein the copper complex is 720mg/L. Therefore, the saturated adsorption capacity of the liquid resin is lower, and the effluent is complexedThe liquid resin changes the mass ratio of the diethylenetriamine penta-methylene phosphonic acid, the 2-hydroxy-5-nonylacetophenone oxime and the salicylaldoxime, namely the liquid resin has smaller content of the diethylenetriamine penta-methylene phosphonic acid and higher content of the salicylaldoxime, the formed network structure is smaller (the molecular weight is relatively lower), and more salicylaldoxime and copper form single-chain chelate independently, so that the whole adsorption capacity and stability of the liquid resin are reduced.
Before the liquid resin tower regeneration process, pure water is used for cleaning the liquid resin, a large amount of COD adhered to the liquid resin is washed, the pure water cleaning flow rate is 15BV/h, the pure water amount is 1BV, then nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin) are used for carrying out liquid resin regeneration, the regeneration time is 7.5min, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Example 8
The liquid resin obtained in comparative example 5 was used for treating copper etching waste liquid (the water content in the copper etching waste liquid was 60m 3 The concentration of copper ions is 4500mg/L, the concentration of complex copper is 2000mg/L, the concentration of hydrogen peroxide is 180000mg/L, the COD content is 60000mg/L, the concentration of fluoride ions is 1000mg/L, the total phosphorus is 500mg/L, and the pH value is high<0.85 Processing, specifically:
(1) Collecting the high-concentration copper-containing wastewater through a pipeline, and then, entering a homogenizing pool, wherein the residence time is 4 hours;
(2) The effluent of the homogenizing pool is fed into a reactor, and the reactor comprises three liquid resin towers, namely a liquid resin tower A, a liquid resin tower B and a liquid resin tower C (the filling amount of the liquid resin in the liquid resin tower A, the liquid resin tower B and the liquid resin tower C is 20m 3 ) Baffles are arranged in the three liquid resin towers and used for increasing the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater firstly enters a liquid resin tower A and a liquid resin tower B which are sequentially connected in series for adsorption, the liquid resin tower A is filled with water, the liquid resin tower B is discharged, and when the liquid resin in the liquid resin tower A is fully adsorbed and saturatedAnd then (after 18 hours of operation), the liquid resin tower A enters a regeneration process, the liquid resin tower B and the liquid resin tower C are connected in series to start adsorption operation, the liquid resin tower B is fed with water, and the liquid resin tower C is discharged with water; after the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters a regeneration process, the liquid resin tower C and the liquid resin tower A are sequentially connected in series to start adsorption operation, the liquid resin tower C is filled with water, and the liquid resin tower A is discharged with water; after the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower C enters a regeneration process, the liquid resin tower A and the liquid resin tower B are sequentially connected in series to start adsorption operation, and the reactor is continuously operated in the mode; after the A+ B, B + C, C +A resin towers are respectively operated for 18 hours, the copper concentration of the system effluent is 2025mg/L, wherein 760mg/L of complex copper is adopted; the reason is that 2-ethylhexyl phosphinic acid has only one phosphorus-oxygen double bond, and forms a hydrogen bond with the hydroxyl in the hydroxyl imine structure C=N-OH of salicylaldoxime, and the formed product is of a single-chain structure, so that the adsorption capacity and stability of the liquid resin to copper are reduced;
before the liquid resin tower regeneration process, pure water is used for cleaning the liquid resin, a large amount of COD adhered to the liquid resin is washed, the pure water cleaning flow rate is 15BV/h, the pure water amount is 1BV, then nonylphenol (the adding amount of nonylphenol is 0.3 times of the mass of the liquid resin) and sulfuric acid with the mass fraction of 20% (the adding volume of sulfuric acid is 1/3 of the volume of the liquid resin) are used for carrying out liquid resin regeneration, the regeneration time is 7.5min, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8BV/h, and the medicine amount is 1BV.
Claims (6)
1. A liquid resin characterized in that: the composite material consists of the following components in parts by weight: 1-2 parts of diethylenetriamine pentamethylene phosphonic acid, 0.5-2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1-2 parts of salicylaldoxime, 0.1-0.2 part of 2, 6-di-tert-butylhydroquinone and 10-20 parts of organic solvent.
2. The method for preparing a liquid resin according to claim 1, comprising the steps of:
(1) The preparation method comprises the steps of (1) stirring and mixing a formula amount of diethylenetriamine penta (methylene phosphonic acid) and 2-hydroxy-5-nonylacetophenone oxime at normal temperature to obtain a mixture;
(2) Adding a formula amount of salicylaldoxime into the mixture in the step (1), and reacting at a high temperature to obtain a product I with a net structure;
(3) Taking 2, 6-di-tert-butylhydroquinone with the formula amount, heating and dissolving, then adding the mixture into a product I for dehydration reaction, and obtaining a product II after the reaction;
(4) Mixing the product II with a formula amount of organic solvent to obtain liquid resin.
3. The method for producing a liquid resin according to claim 2, wherein: in the step (2), the reaction temperature is not lower than 60 ℃.
4. The method for producing a liquid resin according to claim 2, wherein: in the step (3), the heating temperature is 35-40 ℃.
5. The method for regenerating a liquid resin according to claim 1, which is characterized by comprising the following steps: washing the liquid resin with water, adding nonylphenol and sulfuric acid with mass fraction not lower than 15% into the liquid resin, and treating for 5-8 min to obtain regenerated liquid resin.
6. The method for regenerating a liquid resin according to claim 5, wherein: the addition amount of the nonylphenol is 0.2-0.5 times of the mass of the liquid resin; the adding volume of the sulfuric acid is 1/2-1/5 of the volume of the liquid resin.
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| CN116854224A (en) | 2023-10-10 |
| CN115819782A (en) | 2023-03-21 |
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