CN104445469B - A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater - Google Patents
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
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- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F2303/06—Sludge reduction, e.g. by lysis
Abstract
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, relates to electroplating wastewater processing and sludge circulation utilizes.1) during the electroplating wastewater Han phosphor/phosphine is collected in wastewater collection pond；2) will be through step 1) pumping in reaction tank containing phosphor/phosphine electroplating wastewater and electroplating sludge in wastewater collection pond react, method particularly includes: react be collected separately with corresponding metal sludge respectively containing phosphor/phosphine electroplating wastewater, or reacting mixed collection with comprehensive sludge reaction or cross-mixing containing phosphor/phosphine electroplating wastewater；In electroplating sludge in addition to containing heavy metal ion, possibly together with the calcium added in Electroplating Wastewater Treatment, magnesium, ferrum, aluminum plasma；Reacted with the middle phosphor/phosphine acid group containing phosphor/phosphine electroplating wastewater by metal ion in electroplating sludge, form the phosphor/phosphine acid metal salt that dissolubility is less, reach to remove phosphor/phosphine and the purpose of heavy metal ion；3) mud-water separation.Can reduce electroplating sludge generation amount, mud is more easy to filter pressing and moisture content is lower, and treatment cost is low.
Description
Technical field
The present invention relates to electroplating wastewater processing and sludge circulation utilizes, especially relate to one and utilize electroplating sludge to process containing phosphor/phosphine electricity
The method of waste electroplating.
Background technology
Electroplating Wastewater Treatment has dual treatment technique and mixed processing technique.Dual treatment technique is that electroplating wastewater is divided into Nickel-bearing Waste
Water, chemical nickel waste water, acid copper waste water, burnt copper waste water, chromate waste water, acidic and alkaline waste water, comprehensive wastewater etc., according to metal ion
Classification carries out categorised collection and dual treatment；Mixed processing technique is will to be collected separately containing chromium, cyanide wastewater, individually reduction, oxygen
With other waste water mixed processing after change pretreatment.The easy stably reaching standard of dual treatment technique, but Complete Classification collects difficulty, and
The co-precipitation of the broad acid-base in waste water and metal ion cannot be utilized, when waste water contains phosphorous complexant, increase adding of agent
Amount and mud generation amount, increase waste water treatment cost and the salinity of waste water up to standard.Mixed processing technique is simple, but stably reaches
Mark relatively difficult, relatively costly.
The more removal focusing on heavy metal ion of traditional Electroplating Wastewater Treatment, uses ion exchange, chemical reaction, electrolysis etc.
Heavy-metal ion removal.Owing to electroplating wastewater containing various complexants, such as pyrophosphate, cyanogen, citrate, hydroxyl Asia second
Bases diphosphine acid group (HEDP) etc., cause heavy metal ion to be difficult to stably reaching standard.Employing oxidant such as oxidizer containing chlorine, ozone,
The methods such as electrolysis can effectively remove cyanogen root, technology maturation, (ORP/pH control) easy to control；Containing citric acid, phosphor/phosphine acid group,
The electroplating wastewater processing of the ligand such as pyrophosphate, multi-phosphate lacks corresponding engineering automatic control means；Pyrophosphate is acidified
Hydrolysis is the complexant that phosphate radical can eliminate in waste water, but hydrolysis degree is difficult to judge, it is impossible to realize automatically controlling, real
Border application can only add any excess drug, could meet the emission request of heavy metal and total phosphorus.Use in cyanideless electro-plating is coordinated containing phosphine
The methods such as the oxidation of agent such as HEDP, hydrolysis also cannot be thorough, Calx can only be used in a large number to precipitate.
Removal of heavy metal ions in electroplating wastewater is easy, and coordination anion removes difficulty, causes heavy metal ion to stablize
Qualified discharge.Electroplating Wastewater Treatment is progressively converted into the removal of focusing coordination ion from focusing on removal of heavy metal ions.Electroplating wastewater
Administering it is important that heavy metal ion, difficult point is to remove complexant, and key point is categorised collection.
Traditional plating administering method containing phosphor/phosphine electroplating wastewater mainly will contain phosphor/phosphine electroplating wastewater and be collected separately, and use calcium hydroxide
Or calcium chloride or iron salt or aluminium salt, the phosphorous/phosphonate radical in precipitation of phosphorus/phosphine electroplating wastewater and heavy metal ion, although waste water obtains
Administer, but while waste resource, but add the generation amount of electroplating sludge, or the heavy metal ion that use coordination property is higher
Heavy metal ion in agent for capturing heavy-metal ion removal, or electrolysis/light electrolysis removal waste water, but total phosphorus and COD easily surpass
Mark and relatively costly.
The multiplex Chemical Method for Waste Water of Electroplate of comprehensive electroplating enterprise, mainly hydroxide precipitation method, result produces a large amount of mud.
Containing metal ion such as ferrum, aluminum, calcium, magnesium, copper, nickel, zinc, chromium etc. in electroplating sludge, electroplate with containing phosphor/phosphine with electroplating sludge
Waste water reaction, under certain pH value, owing to the metal salt solubilities of phosphor/phosphine acid is less than the dissolving of corresponding metal hydroxides
Degree, displaces hydroxyl with phosphor/phosphine acid group, can make full use of metal in sludge ion and hydroxide ion, also can remove phosphorous
Heavy metal in/phosphine electroplating wastewater and total phosphorus, reduce additional pharmaceutical quantities.
Electroplating sludge belongs to hazardous waste, and main research and application for a long time is the resource of electroplating sludge, i.e. utilize the acid-hatching of young eggs,
The technology such as ammonia leaching process, bioleaching method, smelting process and roasting leaching method extracts valuable heavy metal, or potting ceramic material or magnetic
Property material or harmlessness disposing landfill.
Chinese patent CN102910771A discloses a kind of process technique and the method for high-concentration phosphorus-containing wastewater.By design by highly concentrated
Degree phosphorus-containing wastewater first passes through iron-carbon micro-electrolysis device and first carries out pretreatment, then uses multiple water treatment medicament to compound, adds
Carry out in firsts and seconds flocculation sedimentation tank deepen reaction treatment, then sequentially pass through quartz filter, active carbon filter and
Plate film assembly carries out composite water quality lifting process, thus reaches recycle water standard.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater.
The present invention comprises the following steps:
1) during the electroplating wastewater Han phosphor/phosphine is collected in wastewater collection pond；
2) will be through step 1) pumping in reaction tank containing phosphor/phosphine electroplating wastewater and electroplating sludge in wastewater collection pond react, specifically
Method is: react be collected separately with corresponding metal sludge respectively containing phosphor/phosphine electroplating wastewater, or phosphorous by mixed collection
/ phosphine electroplating wastewater reacts with comprehensive sludge reaction or cross-mixing；In electroplating sludge in addition to containing heavy metal ion, possibly together with plating
The calcium of interpolation, magnesium, ferrum, aluminum plasma in waste water treatment；By metal ion in electroplating sludge and containing in phosphor/phosphine electroplating wastewater
Phosphor/phosphine acid group reacts, and forms the phosphor/phosphine acid metal salt that dissolubility is less, reaches to remove phosphor/phosphine and the purpose of heavy metal ion；
3) mud-water separation.
In step 1) in, described collection can be collected separately or mixed collection；
The described method being collected separately can be: (1) by oxidation-reducibility collect, described by oxidation-reducibility collect include but not
Be limited to be collected separately containing hexavalent chromium wastewater, cyanide wastewater is collected separately；(2) collect by anion or complexant kind, described press
Anion or complexant kind collect include but not limited to burnt copper waste water be collected separately, chemical nickel waste water (phosphorus-containing wastewater, containing coordination
Agent waste water) be collected separately, cyanideless electro-plating waste water Han phosphine is collected separately, pre-treatment waste water (containing polyphosphate waste water) is collected separately；
(3) by producing region and technological process collection, described collection by production region and technological process includes but not limited to pre-treatment waste water
(phosphorus-containing wastewater) is collected separately, the electroplating wastewater containing phosphine is collected separately, burnt copper waste water is collected separately；(4) press administering method to collect,
Described collection by administering method includes but not limited to that pre-treatment waste water is collected separately, the waste water containing phosphine is collected separately, burnt copper waste water is independent
Collect, acid copper waste water is collected separately, cyanide wastewater is collected separately, chromate waste water is collected separately, nickel-containing waste water is collected separately, change
Nickel waste water is collected separately, zinc-containing water is collected separately；
The method of described mixed collection can be: (1) is collected by metal species, and described collection by metal species includes but not limited to acid
Copper and burnt copper waste water mixed collection, chemical nickel waste water and nickel-containing waste water mixed collection；(2) press Acidity of Aikalinity to collect, described by soda acid
Property collect and include but not limited to acid copper waste water and chromate waste water mixed collection, burnt copper waste water and cyanogen copper waste water mixed collection；(3) press
Anion or complexant kind are collected, and described collection by anion or complexant kind includes but not limited to burnt copper waste water, chemical nickel
Waste water (phosphorus-containing wastewater, containing complexant waste water), cyanideless electro-plating are containing in phosphine waste water, pre-treatment waste water (containing polyphosphate waste water) etc.
At least one mixed collection；(4) collecting by production region and technological process, described collection by production region and technological process is wrapped
Include but be not limited to pre-treatment waste water (phosphorus-containing wastewater), containing at least one mixed collection in phosphine electroplating wastewater, burnt copper waste water etc.；
The described electroplating wastewater containing phosphor/phosphine refer to burnt copper electroplating wastewater, chemical nickel electroplating wastewater, containing at least one in phosphine electroplating wastewater etc.；
Phosphorous electroplating wastewater refer to Phos electroplating wastewater, described Phos electroplating wastewater include but not limited to containing pyrophosphate electroplating wastewater,
One in multi-phosphate electroplating wastewater, phosphate radical electroplating wastewater, hypophosphorous acid root electroplating wastewater etc.；The electroplating wastewater containing phosphine refers to organic
Phosphine electroplating wastewater, described organic phosphine electroplating wastewater includes but not limited to containing methylenediphosphonate (MDPA) electroplating wastewater, hydroxyl
Ethylene-diphosphonic acid (HEDP) electroplating wastewater, aminotrimethylene phosphoric acid (ATMP) electroplating wastewater, ethylenediamine tetramethylene phosphine
Acid sodium (EDTMPS) electroplating wastewater, diethylenetriamine pentamethyl phosphonic acids (DTPMPA) electroplating wastewater, triethylene tetramine six
One in methylenephosphonic acid sodium (TETHMPS) electroplating wastewater etc.；
Containing phosphor/phosphine electroplating wastewater, the phosphate radical mass concentration of conversion is 10～80000mg/L, the folding phosphoric acid of burnt copper electroplating wastewater
Root concentration 40～8000mg/L.
In step 2) in, described electroplating sludge can be 1 with the volume ratio containing phosphor/phosphine electroplating wastewater: (1～10)；Described reaction can
Using successive reaction or intermittent reaction, the time of described reaction can be 0.5～2h；Described reaction tank can use up-flow reaction tank,
It can be 0.25～2.5m/h that the electroplating wastewater containing phosphor/phosphine pumps into the raising speed of reaction tank；
The pH that electroplating sludge and the electroplating wastewater containing phosphor/phosphine react can be 6.5～12, the pH that mud and chromium-bearing sludge react can be 7～
9.5, the pH that mud and copper-contained sludge react can be 8.5～10.5, and the pH that mud and nickel-containing sludge react can be 9.5～12, dirty
Mud can be 8.5～11.5 with the pH of comprehensive sludge reaction；
Described electroplating sludge refers to the electroplating integrated mud of mixed processing technique, the copper-contained sludge of dual treatment technique, nickel-containing sludge,
Chromium-bearing sludge, zinc-containing sludge etc., or the mud containing other metal ions；The mud of other metal ions described includes but not limited to
The slurry of the preparation such as calcium hydroxide, magnesium hydroxide；Described electroplating sludge can be the plating after the electroplating sludge of non-filter pressing or filter pressing
Mud, the electroplating sludge of the most non-filter pressing；
The moisture content of described electroplating sludge, between 40%～99.99%, refers in particular to containing hydroxide mud or carbonate containing mud, described
Can be the hydroxide mud of cupric, chromium, nickel, ferrum, aluminum, calcium, magnesium, zinc containing hydroxide mud；When containing of electroplating sludge
When water rate is less than 95%, needing adds water is modulated to muddy；Mud can also use the Calx of powder, quick lime, limestone,
At least one in magnesium oxide, magnesium hydroxide, aluminium polychlorid, bodied ferric sulfate etc. substitutes.
In step 3) in, the concrete grammar of mud-water separation is as follows:
During intermittent reaction, reaction tank doubles as sedimentation tank, and after stirring reaction 0.5～2h, if standing 3～6h, then supernatant enters comprehensively
Wastewater collection pond, mud enters sludge concentration tank；If more than time of repose 6h, then supernatant enters comprehensive wastewater collecting pit, dirty
Mud can be directly entered sludge filter press filter pressing；
During continuous reaction, arranging sedimentation tank after reaction tank, be 2～6h in the time of staying of sedimentation tank, supernatant flows into comprehensive
Wastewater collection pond, mud enters sludge concentration tank or sludge filter press filter pressing from bottom；
During up-flow reaction (available sludge concentration tank transform up-flow reaction tank as), react from up-flow containing phosphor/phosphine electroplating wastewater
Entering bottom pond, raising speed is 0.25～2.5m/h, and mud enters from up-flow reaction tank middle and upper part, and supernatant reacts from up-flow
Top, pond enters comprehensive wastewater collecting pit after flowing out, and mud enters sludge filter press filter pressing from bottom.
When the electroplating wastewater volume containing phosphor/phosphine is less, it is directly entered sludge filter press filter pressing after reaction tank reaction and separates, or centrifuge
Separate, or microfiltration Ultra filtration membrane.
Under suitable pH, the dissolubility of the phosphor/phosphine hydrochlorate of metal is generally less than corresponding metal hydroxides, uses phosphor/phosphine hydrochlorate
Or pyrophosphate reacts with metal hydroxides, while removing phosphor/phosphine acid group, also displace hydroxide ion for waste water treatment.
Due to the fact that the broad acid-base making full use of in electroplating wastewater, with plating treating sludge electroplating wastewater Han phosphor/phosphine, therefore may be used
That reduces in Electroplating Wastewater Treatment saline and alkaline adds, and reduces sludge yield and pharmaceutical quantities, significantly reduces the soluble solid in waste water,
Reducing electroplating sludge generation amount, mud is easier to filter pressing and moisture content is lower, reduces waste water treatment cost, reduces containing in waste water
Salt amount, reduce environmental pollution, lifting waste water reclamation rate and sludge circulation utilization rate, mud can decrement 25%～50%, processing cost
About 50% can be reduced.
Accompanying drawing explanation
Fig. 1 is the flow chart of the embodiment of the present invention.
Fig. 2 is Treatment of Sludge Jiao's copper waste water embodiment flow chart.
Detailed description of the invention
Embodiment 1
It is collected separately in burnt copper waste water collecting pit containing burnt copper waste water, after the regulating water quality water yield.Jiao's copper waste water is pumped into chromate waste water
Sludge concentration tank, waste water pumps into 1/2～3/4 depths of concentration basin, and keeping waste water to rise Flow Velocity is 0.25～2.5m/h, uses pH
Meter (pH ＜ 8.5) controls the burnt copper waste water amount of pumping into.
It is 1: 1～1: 5 that intermittently operated also can operate continuously control mud waste water ratio.When working continuously, pH controls electromagnetic valve control
The mud amount of pumping into processed.
Chemical nickel waste water pumps into nickel-containing sludge concentration basin or comprehensive sludge concentration tank (mud waste water ratio 1: 1～1: 10, pH ＞ 8.5).
Phosphorous cyanideless electro-plating then pumps into (mud waste water ratio 1: 1～1: 10, pH ＜ 10.5) in comprehensive sludge concentration tank.
Newly-built up-flow reaction tank, mud pumps into from Chi Ding, and phosphorus-containing wastewater autoreaction pumps into bottom pond, waste water up-flow speed controlling
0.25～2.5m/h.
Water outlet phosphate concentration 0.10～5mg/L, water outlet total heavy metal ion concentration 0.05～5.0mg/L.
Embodiment 2:
Newly-built or transformation i.e. has chemical processing system, is mixed by a certain percentage with phosphorus-containing wastewater by the mud of sedimentation tank or sludge concentration tank
Close (dirt mud waste water ratio 1: 2), enter reaction tank, use pH meter to control mud or the electroplating wastewater addition Han phosphor/phosphine, mud
Aqueous mixtures enters sedimentation tank precipitation.Water outlet enters in comprehensive collection pond or corresponding wastewater collection pond.Mud enters sludge condensation
Pond concentrates.
For making full use of mud in operating process, keep sludge reflux amount 25%～300%.
Water outlet phosphate concentration ＜ 5mg/L.
Embodiment 3:
The phosphorous discarded tank liquor of pre-electroplating treatment, sludge sump liquor ratio is 5: 1～10: 10, water outlet total phosphorus ＜ 5mg/L, total metal from
Sub-concentration ＜ 5mg/L.
Due to the fact that the broad acid-base making full use of in electroplating wastewater, with plating treating sludge electroplating wastewater Han phosphor/phosphine, therefore subtract
Saline and alkaline in few waste water treatment adds, and reduces sludge yield and pharmaceutical quantities, significantly reduces the soluble solid in waste water, reduces electricity
Plating mud generation amount, reduces waste water treatment cost, reduces the salinity in waste water, reduces environmental pollution, lifting waste water reclamation rate
Cyclic utilization rate with electroplating sludge.
As a example by burnt copper waste water, burnt copper waste water is containing outside Copper pyrophosphate., and possibly together with potassium pyrophosphate, electroplating sludge just administers burnt copper waste water
It is to react with pyrophosphate or phosphate radical with plating metal in sludge ion.
(1) the burnt copper waste water chemical reaction that may be present of chromium-bearing sludge process:
4Cr(OH)3+3K4P2O7=Cr4(P2O7)3+12KOH
2Cr(OH)3+K4P2O7=Cr2(OH)2(P2O7)+4KOH
Cr(OH)3+K4P2O7+H2O=CrHP2O7+4KOH
In mud, the metal ion such as iron content, aluminum there is also similar reaction.After the excessive pyrophosphate in burnt copper waste water is removed,
Losing Coordinate property, Copper pyrophosphate. dissolubility is the least, and copper ion is removed naturally.
(2) the burnt copper waste water chemical reaction that may be present of copper-contained sludge process:
2Cu(OH)2+K4P2O7=Cu2(P2O7)+4KOH
3Cu(OH)2+K4P2O7=Cu3(OH)2(P2O7)+4KOH
3Cu(OH)2+2K4P2O7+2H2O=Cu3(HP2O7)2+8KOH
Nickel-containing sludge, zinc-containing sludge or the calcic of artificial preparation, also can react with burnt copper waste water containing magnesium mud (mud) etc.,
In mud ferrum, the metal ion such as aluminum there is also similar reaction.
Test one: the moisture content 99.8% of chromium-bearing sludge, the copper ion mass concentration in burnt copper waste water is 370mg/L.Take respectively
100ml chromium-bearing sludge is placed in 5 beakers, adds the burnt copper waste water of 10ml, 20ml, 40ml, 60ml, 100ml respectively.
After reaction 30min, test supernatant copper, chromium ion concentration, result such as table 1 respectively.
Table 1
| Beaker is numbered | 1# | 2# | 3# | 4# | 5# |
| Chromium-bearing sludge milliliter number | 100 | 100 | 100 | 100 | 100 |
| Burnt copper waste water milliliter number | 10 | 20 | 40 | 60 | 100 |
| Composite waste copper ion theoretical concentration (mg/L) | 33.6 | 61.7 | 105.7 | 138.8 | 185 |
| Supernatant copper ion concentration (mg/L) after 30min | - | - | 5.3 | 29.5 | 80.2 |
| Copper ion clearance (%) | 100 | 100 | 95 | 78.7 | 56.6 |
| Supernatant phosphate concentration (mg/L) after 30min | - | - | 15.4 | 80 | 114 |
| 30min chromium ion concentration (mg/L) | - | - | 3.1 | 3.9 | 3.2 |
Test two: chromium-bearing sludge and copper ion mass concentration are the burnt copper waste water controlled trial of 62mg/L, result such as table 2.
Table 2
| Beaker is numbered | 1# | 2# | 3# | 4# | 5# |
| Chromium-bearing sludge milliliter number | 10 | 20 | 40 | 60 | 100 |
| Burnt copper waste water milliliter number | 100 | 100 | 100 | 100 | 100 |
| Supernatant copper ion concentration (mg/L) after 30min | 31 | 15 | 2.3 | 0.4 | 0.1 |
| Copper ion clearance (%) | 45 | 71 | 94.8 | 99 | 99.7 |
| 30min chromium ion concentration (mg/L) | 1.09 | 1.01 | 0.14 | 0.03 | 0.01 |
Test three: the moisture percentage in sewage sludge about 99.8% of comprehensive mud, calcic, aluminum, ferrum, copper plasma in mud, burnt copper waste water
In copper ion mass concentration be 370mg/L.Take the comprehensive mud of 100ml respectively to be placed in 5 beakers, add respectively 10ml,
The burnt copper waste water (copper ion concentration 370mg/L) of 20ml, 40ml, 60m, 100ml.After reaction 30min, survey respectively
Examination supernatant copper, chromium ion concentration, result such as table 3.
Table 3
| Beaker is numbered | 1# | 2# | 3# | 4# | 5# |
| Comprehensive mud milliliter number | 100 | 100 | 100 | 100 | 100 |
| Burnt copper waste water milliliter number | 10 | 20 | 40 | 60 | 100 |
| Composite waste copper ion theoretical concentration (mg/L) | 33.6 | 61.7 | 105.7 | 138.8 | 185 |
| Composite waste phosphate radical theoretical concentration (mg/L) | 252 | 463 | 793 | 1041 | 1388 |
| Supernatant copper ion concentration (mg/L) after 30min | 0.56 | 1.29 | 10.06 | 26.88 | 73.7 |
| Copper ion clearance (%) | 98.3 | 97.9 | 90.6 | 80.8 | 60.5 |
| Supernatant phosphate concentration (mg/L) after 30min | - | - | 35 | 67 | 250 |
Test four: copper ion mass concentration is burnt copper waste water and comprehensive mud controlled trial, the result such as table 4 of 62mg/L.
Table 4
| Beaker is numbered | 1# | 2# | 3# | 4# | 5# |
| Comprehensive mud milliliter number | 10 | 20 | 40 | 60 | 100 |
| Burnt copper waste water milliliter number | 100 | 100 | 100 | 100 | 100 |
| Supernatant copper ion concentration (mg/L) after 30min | 24 | 8.5 | 1.3 | 0.4 | 0.1 |
Test five: copper-contained sludge, nickel-containing sludge and burnt copper waste water (copper ion mass concentration 370mg/L).Result of the test such as table 5.
Table 5
Test six: chemical nickel waste water, nickel ion mass concentration is 24mg/L, phosphate concentration 45mg/L.With four class mud 1:1
Mixing, result such as table 6 after reaction 30min.
Table 6
| Mud classification | Chromium-bearing sludge | Copper-contained sludge | Nickel-containing sludge | Comprehensive mud |
| Copper ion concentration (mg/L) | - | - | 0.35 | - |
| Nickel ion concentration (mg/L) | 0.34 | - | - | - |
| Chromium ion concentration (mg/L) | - | - | - | 0.05 |
| Phosphate concentration (mg/L) | 0.12 | 0.45 | 1.34 | 0.06 |
Test seven: containing phosphine electroplating wastewater, lime cream content controls at 1g/L～100g./L, and waste water copper ion concentration is 35mg/L,
Result of the test such as table 7.
Table 7
| Lime milk concentration (g/L) | 3 | 5 | 20 | 100 |
| Copper ion concentration (mg/L) | 0.21 | 2.1 | 4.5 | 10.1 |
Treatment of Sludge electroplating wastewater flow chart Han phosphor/phosphine sees Fig. 1, being collected in wastewater collection pond containing phosphor/phosphine electroplating wastewater, adjusts
After water saving matter and the water yield, pumping into reaction tank, pump into mud in proportion, after reacting 0.5～2h in reaction tank, mud mixture enters
Entering rectangular sedimentation tank, hydraulic detention time 2～6h in sedimentation tank, supernatant enters comprehensive wastewater collecting pit, and mud enters mud
Concentration basin, enters pressure filter and carries out sludge press filtration, and pressure filtration yielding water enters comprehensive wastewater collecting pit, and mud cake is stored.
Treatment of Sludge Jiao's copper waste water flow chart sees Fig. 2, the dual treatment technique of electroplating wastewater produce copper-contained sludge, chromium-bearing sludge,
Nickel-containing sludge, zinc-containing sludge, comprehensive mud etc..Burnt copper waste water is pumped directly into cupric (containing chromium) sludge-tank or mixing-reaction respectively
After-precipitation-solid-liquid separation, mud enters sludge concentration tank, and supernatant enters comprehensive wastewater collecting pit or corresponding cupric or containing chromium
Wastewater collection pond.Treatment of Sludge is similar with burnt copper waste water containing phosphine waste water, chemical nickel waste water, pre-treatment waste water etc. without cyanogen.Work as mud
When cannot balance, the hydroxide such as calcium, magnesium, ferrum, aluminum can be used to substitute.The mud of concentration basin enters pressure filter and carries out mud pressure
Filter, pressure filtration yielding water enters comprehensive wastewater collecting pit, and mud cake is stored.
Claims (8)
1. one kind utilizes electroplating sludge to process the method containing phosphor/phosphine electroplating wastewater, it is characterised in that comprise the following steps:
1) during the electroplating wastewater Han phosphor/phosphine is collected in wastewater collection pond；Described being collected as is collected separately or mixed collection；
The described method that is collected separately is: (1) is collected by oxidation-reducibility, and described collection by oxidation-reducibility includes but do not limit
In being collected separately containing hexavalent chromium wastewater, cyanide wastewater is collected separately；(2) collect by anion or complexant kind, described by the moon
Ion or complexant kind are collected and are included but not limited to that copper waste water is collected separately Jiao, chemical nickel waste water is collected separately, cyanideless electro-plating contains
Phosphine waste water is collected separately, pre-treatment waste water is collected separately；Described chemical nickel waste water is phosphorus-containing wastewater and the waste water Han complexant, described
Pre-treatment waste water is containing polyphosphate waste water；(3) by producing region and technological process collection, described by producing region and technique stream
Journey is collected and is included but not limited to that pre-treatment waste water is collected separately, the electroplating wastewater containing phosphine is collected separately, burnt copper waste water is collected separately；Institute
Stating pre-treatment waste water is phosphorus-containing wastewater；(4) pressing administering method to collect, described collection by administering method includes but not limited to pre-treatment
Waste water is collected separately, the waste water containing phosphine is collected separately, burnt copper waste water is collected separately, acid copper waste water is collected separately, cyanide wastewater is independent
Collect, chromate waste water is collected separately, nickel-containing waste water is collected separately, chemical nickel waste water is collected separately, zinc-containing water is collected separately；
The method of described mixed collection is: (1) is collected by metal species, and described collection by metal species includes but not limited to acid copper
With burnt copper waste water mixed collection, chemical nickel waste water and nickel-containing waste water mixed collection；(2) press Acidity of Aikalinity to collect, described by Acidity of Aikalinity
Collection includes but not limited to acid copper waste water and chromate waste water mixed collection, burnt copper waste water and cyanogen copper waste water mixed collection；(3) by the moon
Ion or complexant kind are collected, and described collection by anion or complexant kind includes but not limited to that burnt copper waste water, chemical nickel are given up
Water, cyanideless electro-plating are containing at least two mixed collection in phosphine waste water, pre-treatment waste water；Described chemical nickel waste water be phosphorus-containing wastewater and
Containing complexant waste water, described pre-treatment waste water is containing polyphosphate waste water；(4) by producing region and technological process collection, described
Collect by production region and technological process and include but not limited to pre-treatment waste water, containing at least two in phosphine electroplating wastewater, burnt copper waste water
Plant mixed collection；Described pre-treatment waste water is phosphorus-containing wastewater
2) will be through step 1) pumping in reaction tank containing phosphor/phosphine electroplating wastewater and electroplating sludge in wastewater collection pond react, specifically
Method is: react be collected separately with corresponding metal sludge respectively containing phosphor/phosphine electroplating wastewater, or phosphorous by mixed collection
/ phosphine electroplating wastewater and comprehensive sludge reaction；
3) mud-water separation.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 1) in, the described electroplating wastewater containing phosphor/phosphine refer to burnt copper electroplating wastewater, chemical nickel electroplating wastewater, containing in phosphine electroplating wastewater at least
A kind of；Phosphorous electroplating wastewater refers to that Phos electroplating wastewater, described Phos electroplating wastewater include but not limited to containing pyrophosphate plating
One in waste water, multi-phosphate electroplating wastewater, phosphate radical electroplating wastewater, hypophosphorous acid root electroplating wastewater；The electroplating wastewater containing phosphine refers to
Organic phosphine electroplating wastewater, described organic phosphine electroplating wastewater includes but not limited to containing methylenediphosphonate electroplating wastewater, hydroxy ethylidene two
Phosphonic acids electroplating wastewater, aminotrimethylene phosphoric acid electroplating wastewater, sodium ethylenediamine tetramethylenephosphonate electroplating wastewater, diethylenetriamine
One in pentamethyl phosphonic acids electroplating wastewater, Triethylene-tetramine Hexmethanephonic Acid sodium electroplating wastewater.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 2), in, described electroplating sludge is 1 with the volume ratio containing phosphor/phosphine electroplating wastewater: (1～10)；Described reaction uses successive reaction
Or intermittent reaction, the time of described reaction is 0.5～2h；Described reaction tank uses up-flow reaction tank, containing phosphor/phosphine electroplating wastewater pump
The raising speed entering reaction tank is 0.25～2.5m/h.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 2), in, the pH that electroplating sludge and the electroplating wastewater containing phosphor/phosphine react is 6.5～12.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 2) in, described electroplating sludge refers to the electroplating integrated mud of mixed processing technique, the copper-contained sludge of dual treatment technique, nickeliferous
Mud, chromium-bearing sludge, zinc-containing sludge, or the mud containing other metal ions；The mud of other metal ions described include but not
It is limited to calcium hydroxide, the slurry of magnesium hydroxide preparation；Described electroplating sludge is the plating after the electroplating sludge of non-filter pressing or filter pressing
Mud.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that described
Electroplating sludge is the electroplating sludge of non-filter pressing.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 2), in, the moisture content of described electroplating sludge, between 40%～99.99%, refers to containing hydroxide mud or carbonate containing mud,
Described containing the hydroxide mud that hydroxide mud is cupric, chromium, nickel, ferrum, aluminum, calcium, magnesium, zinc；When electroplating sludge
When moisture content is less than 95%, needing adds water is modulated to muddy.
A kind of method utilizing electroplating sludge process to contain phosphor/phosphine electroplating wastewater, it is characterised in that in step
Rapid 3), in, the concrete grammar of mud-water separation is as follows:
During intermittent reaction, reaction tank doubles as sedimentation tank, and after stirring reaction 0.5～2h, if standing 3～6h, then supernatant enters comprehensively
Wastewater collection pond, mud enters sludge concentration tank；If more than time of repose 6h, then supernatant enters comprehensive wastewater collecting pit, dirty
Mud is directly entered sludge filter press filter pressing；
During continuous reaction, arranging sedimentation tank after reaction tank, be 2～6h in the time of staying of sedimentation tank, supernatant flows into comprehensive
Wastewater collection pond, mud enters sludge concentration tank or sludge filter press filter pressing from bottom；
During up-flow reaction, entering bottom up-flow reaction tank containing phosphor/phosphine electroplating wastewater, raising speed is 0.25～2.5m/h, mud
Entering from up-flow reaction tank middle and upper part, supernatant enters comprehensive wastewater collecting pit, mud after up-flow reaction tank top is flowed out
Sludge filter press filter pressing is entered from bottom；Up-flow reaction tank during up-flow reaction uses sludge concentration tank；
When the electroplating wastewater volume containing phosphor/phosphine is less, it is directly entered sludge filter press filter pressing after reaction tank reaction and separates, or centrifuge
Separate, or microfiltration Ultra filtration membrane.
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