CN111018182A - Recycling process of cyaniding cadmium plating electroplating rinsing water - Google Patents
Recycling process of cyaniding cadmium plating electroplating rinsing water Download PDFInfo
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- CN111018182A CN111018182A CN201911323503.1A CN201911323503A CN111018182A CN 111018182 A CN111018182 A CN 111018182A CN 201911323503 A CN201911323503 A CN 201911323503A CN 111018182 A CN111018182 A CN 111018182A
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- cadmium plating
- cyanide
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- ozone oxidation
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- 238000007747 plating Methods 0.000 title claims abstract description 55
- 238000009713 electroplating Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000008237 rinsing water Substances 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 22
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 28
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- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 238000001471 micro-filtration Methods 0.000 claims abstract description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 16
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 16
- 239000013505 freshwater Substances 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
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- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
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- 238000005406 washing Methods 0.000 claims description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 16
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 15
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- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
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- 239000002244 precipitate Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 3
- -1 quaternary ammonium group styrene series Chemical class 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000010170 biological method Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a recycling process of cyanide cadmium plating electroplating rinse water, which comprises the steps of adjusting the pH value of the cyanide cadmium plating electroplating rinse water to be treated to 6-8, introducing ozone, reacting under the action of an ozone oxidation catalyst, completely oxidizing cyanide ions in wastewater, filtering by adopting a microfiltration system to obtain solid-containing concentrated water and fresh water, adjusting the pH value of the fresh water to 10-11 to precipitate metal cadmium, separating by adopting a precision filter, treating filtrate by strong acid H-type cation exchange resin and strong base OH-type anion exchange resin in sequence, and returning to a cyanide cadmium plating rinse tank for production and cleaning. The invention adopts the catalyst with Cu/Ce as the active center to improve the ozone oxidation efficiency and save the cost; secondly, the purposes of catalyst recycling and solid interception are realized by adopting different separation effects of a microfiltration membrane and a precision filter; finally, the anion-cation resin combined system is adopted to remove inorganic anions and cations in the system, reduce secondary pollution and realize the recycling of the treated rinsing water.
Description
Technical Field
The invention belongs to the field of industrial electroplating wastewater treatment, and particularly relates to a recycling process of cyanide cadmium plating electroplating rinsing water.
Background
Cyanide is used as the most excellent complexing agent, has extremely high complexing ability, and the electroplating solution consisting of the cyanide complex has excellent performance, and has the advantages of stable components, strong conductivity, high anodic dissolution and cathodic polarization efficiency, delicate and uniform product coating and strong binding force.
Cyanide cadmium plating electroplating rinsing wastewater contains cyanide ions and heavy metal ions, belongs to highly toxic wastewater, and brings huge risk potential to production and environmental safety. At present, the traditional treatment methods mainly comprise a NaClO secondary cyanogen breaking treatment method, a hydrogen peroxide method, an acidification-volatilization neutralization method, an air method and the like. In recent years, new technologies such as a membrane method, a biological method, a plasma method, a plant absorption method, and a polysulfide treatment method have been used for treating cyanide cadmium plating rinse water. However, in the practical application process, large-scale engineering application is difficult to perform due to the restriction of operational reliability and economic benefits.
The ozone oxidation treatment technology is to oxidize organic matters or inorganic matters in water or wastewater by taking ozone as a strong oxidant so as to achieve the aims of disinfection, oxidation or decoloration. Ozone is a strong oxidant, has the oxidation capacity second to fluorine, has the advantages of strong oxidation capacity, high reaction speed, no secondary pollution and the like, and is an ideal green oxidant. However, the requirement of wastewater treatment is difficult to achieve by simple ozone oxidation, and especially the development goal of miniaturization and efficiency maximization of equipment advocated in the water treatment industry in recent years becomes the focus of research on how to improve the ozone oxidation efficiency in the water treatment industry at present.
The invention patent application CN102626629A discloses a supported metal oxide ozone catalytic oxidation catalyst which takes a common ceramic filter ball as a carrier and supports NiO, and carries out oxidation treatment on p-nitrophenol, and the treatment efficiency can reach more than 80 percent in 70 min. The penxinping takes ozone as an oxidant, researches the ozone oxidation research of the ozone on gold ore cyanide slag under the condition of not adding any other catalyst, the pH value is 7, and the maximum removal rate of 96.3 percent of free cyanogen and 92.3 percent of total cyanogen can be realized in 75 min. Active alumina ceramic balls are used as a carrier, Mn-Ce is used as a load metal, the oxidation effect of ozone on coal chemical industry wastewater is researched, and researches on different load amounts, different metal ratios, different roasting temperatures and different roasting times find that the catalyst prepared by using the load metal Mn, Ce and Mn of 1% and 1% at the roasting temperature of 400 ℃ for 3 hours can obtain the best catalytic effect.
Disclosure of Invention
The invention aims to provide a recycling process of cyanide cadmium plating electroplating rinsing water, which integrates an ozone oxidation technology and a chemical treatment technology, realizes recycling of cyanide cadmium plating rinsing water by adopting oxidation-precipitation-separation-ion exchange, realizes clean production and has higher application value.
The purpose of the invention is realized by the following technical scheme:
a process for reclaiming the electroplating rinse water of cyaniding cadmium plating includes such steps as regulating pH value, oxidizing by ozone, deposition, solid-liquid separation and ion exchange. The method specifically comprises the following steps: adjusting the pH value of the cyanide cadmium plating electroplating rinse water to be treated to 6-8, introducing ozone, performing ozone oxidation treatment under the action of an ozone oxidation catalyst, completely oxidizing cyanide ions in wastewater, filtering by adopting a microfiltration system to obtain solid-containing concentrated water and fresh water, adjusting the pH value of the fresh water to 10-11 to precipitate metal cadmium, separating by adopting a precision filter, sequentially treating filtrate by using strong-acid H-type cation exchange resin and strong-base OH-type anion exchange resin, and returning the effluent to a cyanide cadmium plating rinse tank for production and cleaning, wherein the effluent is neutral and meets the requirements of the cyanide cadmium plating rinse water.
The ozone oxidation catalyst is a catalyst which takes active carbon as a carrier and takes Cu/Ce as an active center.
The ozone oxidation catalyst is prepared by the following method: performing alkali washing and acid washing treatment on the activated carbon, and drying; mixing the cleaned activated carbon with a mixed solution of copper chloride and cerium chloride according to a mass ratio of 1: 10-20, stirring and mixing for 10-15 min, filtering, and roasting the solid at a high temperature of 300-400 ℃ for 4-6 h to obtain the ozone oxidation catalyst.
The active carbon is coal-made active carbon with 60-80 meshes and an iodine value of 400-800.
The alkali washing and acid washing treatment of the activated carbon comprises the following steps: ammonia water with the mass fraction of 5% is used for alkali washing, the amount of the alkali washing is 150% of the mass of the activated carbon, and the filtrate is washed by clean water after the alkali washing until the filtrate is neutral; and then pickling with 5% hydrochloric acid, wherein the pickling amount is 150% of the mass of the activated carbon, cleaning with clear water after pickling until the filtrate is neutral, and drying.
The mass ratio of the copper chloride to the cerium chloride is 5-10: 1, and the total mass fraction of the copper chloride and the cerium chloride in the aqueous solution is 1-5%.
The volume-mass ratio of the cyanided cadmium plating electroplating rinsing water to be treated to the ozone oxidation catalyst is 100: 1-5.
The air inflow of the ozone is 5-10L/t wastewater/min, and the retention time is 10-20 min.
The water yield of the microfiltration membrane of the microfiltration system is 60-85%.
The flow rate of the filtrate passing through the strong-acid H-type cation exchange resin is 3-10 BV/H, and the flow rate of the filtrate passing through the strong-base OH-type anion exchange resin is 3-10 BV/H.
The strong-acid H-type cation exchange resin is strong-acid sulfonic polystyrene H-type cation exchange resin; the strongly basic OH type anion exchange resin is strongly basic quaternary ammonium group styrene series OH type anion exchange resin.
The invention relates to a recycling process of cyaniding cadmium plating electroplating rinsing water, which comprises the following steps:
adjusting the pH value of cyanide cadmium plating electroplating rinsing water to be treated to 6-8, introducing the cyanide cadmium plating electroplating rinsing water into an ozone oxidation reaction kettle, introducing ozone from the bottom at the air input of 5-10L/t wastewater/min, allowing the cyanide cadmium plating electroplating rinsing water to stay for 10-20 min, and completely oxidizing cyanide ions in the wastewater after ozone oxidation treatment;
and (2) filtering the material obtained by ozone oxidation by using a microfiltration system to obtain solid-containing concentrated water and fresh water, returning the solid-containing concentrated water to the ozone oxidation reaction kettle, adjusting the pH value of the fresh water to 10-11 to precipitate the metal cadmium, separating by using a precision filter, treating the solids externally, treating the filtrate by using strong-acid H-type cation exchange resin and strong-base OH-type anion exchange resin at the flow rate of 3-10 BV/H in sequence, and returning the filtrate to a cyanide cadmium plating rinsing water tank for production and cleaning, wherein the effluent is neutral and meets the requirements of cyanide cadmium plating rinsing water.
The ozone oxidation reaction degree is a conventional pressure-resistant reaction kettle.
The invention has the beneficial effects that:
according to the invention, through the treatment steps of oxidation-precipitation-separation-ion exchange, firstly, the catalyst with Cu/Ce as an active center is adopted to improve the ozone oxidation efficiency, so that metal cadmium cations and cyanide anions in wastewater can be effectively removed, and the cost is saved; secondly, the purposes of catalyst recycling and solid interception are realized by using different separation effects of a microfiltration membrane and a precision filter; finally, the anion-cation resin combined system is adopted to remove inorganic anions and cations in the system, reduce secondary pollution and realize the recycling of the treated rinsing water.
The method has high degree of continuity and good quality of effluent, and can effectively solve the problem that the quality of plated parts is influenced by cyanide cadmium plating reuse water.
Drawings
FIG. 1 is a flow chart of the recycling process of cyanide cadmium plating electroplating rinse water.
In figure 1, 1-a first pH adjusting tank, 2-an ozone oxidation reaction kettle, 3-an ozone generator, 4-a catalyst dosing box, 5-a microfiltration system, 6-a second pH adjusting tank, 7-a precision filter, 8-a cation exchange resin tank and 9-an anion exchange resin tank.
Detailed Description
The technical solution of the present invention will be described in detail by the following embodiments.
Example 1
Preparation of ozone catalyst
Selecting coal-made activated carbon with the particle size of 60 meshes and the iodine value of 400, carrying out alkaline washing by adopting ammonia water with the mass fraction of 5%, wherein the alkaline washing amount is 150% of the mass of the activated carbon, and cleaning by adopting clear water after the alkaline washing is finished until filtrate is neutral; and then pickling with 5% hydrochloric acid, wherein the pickling amount is 150% of the mass of the activated carbon, cleaning with clear water after pickling until the filtrate is neutral, and drying the solid at 80 ℃ for later use.
Mixing the cleaned activated carbon with a mixed aqueous solution of copper chloride and cerium chloride (the mass ratio of the copper chloride to the cerium chloride is 5:1, and the total mass fraction of the copper chloride and the cerium chloride is 1%) in a mass ratio of 1:10, fully stirring for 10min, filtering, and roasting the solid at 300 ℃ for 4h to obtain the ozone oxidation catalyst.
Recycling process of cyanide cadmium plating electroplating rinsing water
As shown in figure 1, adjusting the pH value of cyanide cadmium plating electroplating rinse water to be treated to 6.5 in a first pH adjusting tank 1, entering an ozone oxidation reaction kettle, adding an ozone oxidation catalyst with 1% of the mass of the wastewater from a catalyst adding tank 4, preparing ozone by an ozone generator 3, continuously introducing the ozone from the bottom of the reaction kettle according to the air inflow of 10L/t wastewater/min, staying for 20min, and discharging redundant gas from the top of the reaction kettle; the material obtained by the reaction enters a microfiltration system 5, the water obtaining rate of the microfiltration membrane is 60%, concentrated water and fresh water containing solids are obtained by separation, the concentrated water containing the solids returns to the ozone reaction kettle, the fresh water enters a second pH adjusting tank 6, and the pH is adjusted to 10 to form a precipitate; the mixed solution with the precipitate is passed through a precision filter 7 for separation, the solid is treated outside, the filtrate passes through a cation exchange resin tank (001 × 7(732) R strong acid cation exchange resin) and an anion exchange resin tank 9(201 × 7(717) strong base anion exchange resin) at the flow rate of 3BV/h in sequence, and the concentration of the metal cadmium and the total cyanogen in the effluent is detected, and the result is shown in Table 1.
TABLE 1 treatment effect of cyaniding cadmium plating electroplating rinsing water
| Item | pH | Cadmium (mg/L) | Total cyanogen (mg/L) |
| Before treatment | 11.2 | 85.32 | 325.4 |
| After treatment | 7.4 | 0.01 | 0.02 |
Example 2
Preparation of ozone catalyst
Selecting coal-made activated carbon with the particle size of 80 meshes and the iodine value of 800, carrying out alkaline washing by adopting ammonia water with the mass fraction of 5%, wherein the alkaline washing amount is 150% of the mass of the activated carbon, and cleaning by adopting clear water after the alkaline washing is finished until filtrate is neutral; and then pickling with 5% hydrochloric acid, wherein the pickling amount is 150% of the mass of the activated carbon, cleaning with clear water after pickling until the filtrate is neutral, and drying the solid at 80 ℃ for later use.
Mixing the cleaned activated carbon with a mixed aqueous solution of copper chloride and cerium chloride (the mass ratio of the copper chloride to the cerium chloride is 10:1, and the total mass fraction of the copper chloride and the cerium chloride is 5%) in a mass ratio of 1:20, fully stirring for 15min, filtering, and roasting the solid at 400 ℃ for 6h to obtain the ozone oxidation catalyst.
Recycling process of cyanide cadmium plating electroplating rinsing water
Adjusting the pH value of the cyanide cadmium plating electroplating rinsing water to be treated to 7.5 in a first pH adjusting tank 1, feeding the cyanide cadmium plating electroplating rinsing water into an ozone oxidation reaction kettle 2, adding an ozone oxidation catalyst with 5% of the mass of the wastewater from a catalyst adding box 4, preparing ozone by an ozone generator 3, continuously introducing the ozone from the bottom of the reaction kettle according to the air inflow of 5L/t wastewater/min, staying for 10min, and discharging redundant gas from the top of the reaction kettle; the material obtained by the reaction enters a microfiltration system 5, the water obtaining rate of the microfiltration membrane is 85%, concentrated water and fresh water containing solids are obtained by separation, the concentrated water containing the solids returns to the ozone reaction kettle, the fresh water enters a second pH adjusting tank 6, and the pH is adjusted to 11 to form a precipitate; the mixed solution with the precipitate is passed through a precision filter 7 for separation, the solid is treated outside, the filtrate passes through a cation exchange resin tank (001 × 7(732) R strong acid cation exchange resin) and an anion exchange resin tank 9(201 × 7(717) strong base anion exchange resin) at the flow rate of 10BV/h in sequence, and the concentration of the metal cadmium and the total cyanogen in the effluent is detected, and the result is shown in Table 2.
TABLE 2 treatment effect of cyaniding cadmium plating electroplating rinsing water
| Item | pH | Cadmium (mg/L) | Total cyanogen (mg/L) |
| Before treatment | 10.9 | 107.3 | 288.73 |
| After treatment | 7.2 | ND | 0.01 |
Example 3
Preparation of ozone catalyst
Selecting coal-made activated carbon with the particle size of 70 meshes and the iodine value of 600, carrying out alkaline washing by adopting ammonia water with the mass fraction of 5%, wherein the alkaline washing amount is 150% of the mass of the activated carbon, and cleaning by adopting clear water after the alkaline washing is finished until filtrate is neutral; and then 5% hydrochloric acid is adopted for cleaning, the acid cleaning amount is 150% of the mass of the active carbon, clean water is adopted for cleaning after the acid cleaning is finished, the filtrate is cleaned until the filtrate is neutral, and the solid is dried at 80 ℃ for later use.
Mixing the cleaned activated carbon with a mixed aqueous solution of copper chloride and cerium chloride (the mass ratio of the copper chloride to the cerium chloride is 7:1, and the total mass fraction of the copper chloride and the cerium chloride is 3%) in a mass ratio of 1:15, fully stirring for 12min, filtering, and roasting the solid at 350 ℃ for 5h to obtain the ozone oxidation catalyst.
Recycling process of cyanide cadmium plating electroplating rinsing water
Adjusting the pH value of the cyanide cadmium plating electroplating rinsing water to be treated to 7 in a first pH adjusting tank 1, feeding the cyanide cadmium plating electroplating rinsing water into an ozone oxidation reaction kettle 2, adding 3% of ozone oxidation catalyst by mass of wastewater from a catalyst adding box 4, preparing ozone by an ozone generator 3, continuously introducing the ozone from the bottom of the reaction kettle according to the air inflow of 8L/t wastewater/min, staying for 15min, and discharging redundant gas from the top of the reaction kettle; the material obtained by the reaction enters a microfiltration system 5, the water obtaining rate of the microfiltration membrane is 70%, concentrated water and fresh water containing solids are obtained by separation, the concentrated water containing the solids returns to the ozone reaction kettle, the fresh water enters a second pH adjusting tank 6, and the pH is adjusted to 10.5 to form a precipitate; the mixed solution with the precipitate was passed through a microfilter 7 for separation, the solid was subjected to a treatment, the filtrate was passed through a cation exchange resin tank (001 × 7(732) R strongly acidic cation exchange resin) and an anion exchange resin tank 9(201 × 7(717) strongly basic anion exchange resin) at a flow rate of 7BV/h in this order, and the concentrations of metallic cadmium and total cyanogen were measured in the effluent, as shown in table 3.
Comparative example 1
Referring to example 3, the treatment effect of the cyanide cadmium plating electroplating rinse water was examined without using the ozone oxidation catalyst under otherwise unchanged operating conditions, and the specific results are shown in Table 3.
Comparative example 2
Referring to the preparation method of the ozone catalyst in the embodiment 3, the Mn/Ce-loaded ozone oxidation catalyst is prepared by replacing copper chloride with manganese chloride with equal mass; other operation conditions are not changed, the treatment effect of the Mn/Ce-loaded ozone oxidation catalyst on the cyaniding cadmium plating electroplating rinsing water is examined by referring to the recycling process of the cyaniding cadmium plating electroplating rinsing water in the embodiment 3, and the specific result is shown in the table 3.
TABLE 3 treatment effect of cyaniding cadmium plating electroplating rinsing water
Claims (10)
1. A recycling process of cyaniding cadmium plating electroplating rinsing water is characterized by comprising the following steps: adjusting the pH value of cyanide cadmium plating electroplating rinsing water to be treated to 6-8, introducing ozone, performing ozone oxidation treatment under the action of an ozone oxidation catalyst, completely oxidizing cyanide ions in wastewater, filtering by adopting a microfiltration system to obtain solid-containing concentrated water and fresh water, adjusting the pH value of the fresh water to 10-11 to precipitate metal cadmium, separating by adopting a precision filter, treating filtrate by strong acid H-type cation exchange resin and strong base OH-type anion exchange resin in sequence, and returning the filtrate to a cyanide cadmium plating rinsing tank for production and cleaning.
2. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, characterized in that the ozone oxidation catalyst is a catalyst with activated carbon as a carrier and Cu/Ce as an active center.
3. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1 or 2, characterized in that the ozone oxidation catalyst is prepared by the following method: performing alkali washing and acid washing treatment on the activated carbon, and drying; mixing the cleaned activated carbon with a mixed solution of copper chloride and cerium chloride according to a mass ratio of 1: 10-20, stirring and mixing for 10-15 min, filtering, and roasting the solid at a high temperature of 300-400 ℃ for 4-6 h to obtain the ozone oxidation catalyst.
4. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 3, characterized in that the activated carbon is coal-made activated carbon with 60-80 meshes and iodine value of 400-800.
5. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 3, characterized in that the mass ratio of the copper chloride to the cerium chloride is 5-10: 1, and the total mass fraction of the copper chloride and the cerium chloride in the aqueous solution is 1-5%.
6. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, characterized in that the volume-to-mass ratio of the cyanide cadmium plating electroplating rinse water to be treated and the ozone oxidation catalyst is 100: 1-5.
7. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, characterized in that the air input of the ozone is 5-10L/t/min, and the retention time is 10-20 min.
8. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, wherein the water yield of the microfiltration membrane of the microfiltration system is 60-85%.
9. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, wherein the flow rate of the filtrate passing through the strong acid H-type cation exchange resin is 3-10 BV/H, and the flow rate of the filtrate passing through the strong base OH-type anion exchange resin is 3-10 BV/H.
10. The recycling process of cyanide cadmium plating electroplating rinse water according to claim 1, characterized by comprising the following steps:
adjusting the pH value of cyanide cadmium plating electroplating rinsing water to be treated to 6-8, introducing the cyanide cadmium plating electroplating rinsing water into an ozone oxidation reaction kettle, introducing ozone from the bottom at the air input of 5-10L/t wastewater/min, allowing the cyanide cadmium plating electroplating rinsing water to stay for 10-20 min, and completely oxidizing cyanide ions in the wastewater after ozone oxidation treatment;
and (2) filtering the material obtained by ozone oxidation by using a microfiltration system to obtain solid-containing concentrated water and fresh water, returning the solid-containing concentrated water to the ozone oxidation reaction kettle, adjusting the pH value of the fresh water to 10-11 to precipitate the metal cadmium, separating by using a precision filter, treating the solids externally, treating the filtrate by using strong-acid H-type cation exchange resin and strong-base OH-type anion exchange resin at the flow rate of 3-10 BV/H in sequence, and returning the filtrate to a cyanide cadmium plating rinsing water tank for production and cleaning, wherein the effluent is neutral and meets the requirements of cyanide cadmium plating rinsing water.
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