CN104609615B - A kind of processing method containing heavy metal surface treatment waste water - Google Patents
A kind of processing method containing heavy metal surface treatment waste water Download PDFInfo
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- CN104609615B CN104609615B CN201510080262.8A CN201510080262A CN104609615B CN 104609615 B CN104609615 B CN 104609615B CN 201510080262 A CN201510080262 A CN 201510080262A CN 104609615 B CN104609615 B CN 104609615B
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Abstract
The invention discloses a kind of processing method containing heavy metal surface treatment waste water, through wastewater collection, primary first-order equation operation is added sodium hydroxide and is removed phosphate radical, secondary response operation is added sodium hydroxide and is removed aluminium ion, through micro-electrolysis reaction operation, the heavy metal ion in composite waste is reduced again, last passivated reaction process adds ferrous sulfate and sodium hydroxide and CSE reagent, makes the heavy metal ion reaction in composite waste form spinel type ferrite precipitation and discharges.The present invention avoids the generation of calcium precipitation, it is achieved that iron phosphate and the recycling of aluminium hydroxide, and the final mud produced is mainly ferrite, and its Stability Analysis of Structures is insoluble in acid-alkali salt, non-secondary pollution, and dehydration property is good, it is easy to separate.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of processing method containing heavy metal surface treatment waste water.
Background technology
In automobile industry, the surface of auto parts and components comprehend generation a large amount of waste water, in waste water containing sulphuric acid, phosphoric acid,
Chromic acid, nickel, aluminum, Organic substance etc., pH value of waste water is relatively low.At present, producer is generally share split to the processing mode of waste water
Rear employing Calx neutralization precipitation method.
This processing method has the disadvantages that
1, the nertralizer owing to using is Calx, causes not containing only in mud a large amount of metal hydroxides, possibly together with greatly
The amount calcium salt based on calcium sulfate, sludge quantity is big and hydrophobicity is poor, solid-liquid separation difficulty;
2, waste water share split processes and causes equipment investment big, complex process;
3, due to the sludge containing heavy metal poor stability processed with hydroxide form, easily return under acid condition neutral
Molten, cause secondary pollution, therefore such mud to belong to danger useless, need follow-up trust to be correlated with qualification processed in units, somewhat expensive;
When 4, processing containing chromic acid waste, need to first add reducing agent and Cr (VI) is reduced to Cr (III), then alkaline chemical precipitation.
Disadvantages mentioned above constrains the application of Calx neutralization precipitation method, also processes to waste water and brings inevitable technical barrier,
Need the new technical scheme of employing badly to solve.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides a kind of flow process to be simple and convenient to operate,
With low cost and can stably reaching standard, and realize the place containing heavy metal surface treatment waste water of sewage sludge harmlessness, resource simultaneously
Reason method.
Technical scheme: for achieving the above object, the present invention adopts the following technical scheme that
A kind of processing method containing heavy metal surface treatment waste water, comprises the following steps:
1) wastewater collection: each stock waste water merges in regulating reservoir, forms composite waste, regulates the water of described composite waste
The matter water yield, the water quality of described composite waste is phosphate≤30000mg/L, aluminum≤350mg/L, chromium≤350mg/L, copper
≤ 350mg/L, nickel≤350mg/L;
2) primary first-order equation operation: described composite waste enters primary first-order equation pond, adds sulphuric acid in described primary first-order equation pond
Ferrum, described iron sulfate and the phosphate radical in composite waste react generation iron phosphate precipitation;Described primary first-order equation pond is also added with
Sodium hydroxide, regulates pH;
In described primary first-order equation pond, reacted suspension enters primary sedimentation basin, and after standing sedimentation, supernatant enters secondary
Reaction tank, bottom precipitation is discharged;
3) secondary response operation: add sodium hydroxide in described secondary response pond, regulates pH, and reacts raw with aluminium ion
Become aluminum hydroxide precipitation;
In described secondary response pond, reacted suspension enters secondary sedimentation tank, and after standing sedimentation, supernatant enters micro-electricity
Solving reactor, bottom precipitation is discharged;
4) micro-electrolysis reaction operation: carry out aeration in described micro-electrolysis reactor, aeration rate is 5L/min, described electrolysis
Reactor adds sulphuric acid, regulates pH, carry out micro-electrolysis reaction, the heavy metal ion in composite waste is reduced;
The reacted suspension of described electrolysis reactor enters passivation pool;
5) passivation reaction operation: add ferrous sulfate in described passivation pool, adds sodium hydroxide regulation pH, and adds
CSE reagent, stirring, make the heavy metal ion reaction in composite waste form spinel type ferrite precipitation;
The reacted suspension of described passivation pool enters three sedimentation tanks, after standing sedimentation, supernatant qualified discharge, bottom
Precipitation is discharged.
Further, in the present invention, step 2) in, described primary first-order equation pond is added sodium hydroxide, regulates pH
Value is 1.8-2.0;Arranging the time of staying is 2 hours.
Further, in the present invention, step 3) in, described secondary response pond is added sodium hydroxide, regulates pH
Value is for 3.2-3.5, and arranging the time of staying is 30min.
Further, in the present invention, step 4) in, described micro-electrolysis reactor adds sulphuric acid, regulates pH value
For 2.0-3.0.
Further, in the present invention, step 4) in, arranging the time of staying in described micro-electrolysis reactor is 2.0-3.0h,
Keep ORP < 300mv.
Further, in the present invention, step 4) in, described micro-electrolysis reactor is provided with micro-electrolysis stuffing, described
The proportion of micro-electrolysis stuffing is 1.1 tons/m3, specific surface area is 1.2m2/ g, voidage is about 65%, and described light electrolysis is filled out
Material each component by mass percentage be respectively Fe:75-85%, C:10-20%, catalyst: 5%.
Further, in the present invention, step 5) in, described passivation pool adds ferrous sulfate, makes in composite waste
The ratio i.e. T of the amount of materialFe: TMReaching 5~8:1, described M is heavy metal ion, including Cr3+、Ni2+;Add
Sodium hydroxide regulation pH to 9.5-10.0, and add the CSE reagent of 1-3ppm;Described passivation pool keeps
ORP<280mv。
Further, in the present invention, described secondary sedimentation tank and three sedimentation tanks add the PAM of 3~5 ‰;Described
PAM is stored in PAM storage tank, and PAM storage tank carries PAM, PAM through No. four dosing pumps to described secondary sedimentation tank 15
Storage tank carries PAM through No. nine dosing pumps to described three sedimentation tanks.
Further, in the present invention, the hydrogen-oxygen added in described primary first-order equation pond, secondary response pond and described passivation pool
Change sodium be all from sodium hydroxide storage tank, described sodium hydroxide storage tank through a dosing pump to described primary first-order equation pond carry hydrogen-oxygen
Change sodium, described sodium hydroxide storage tank through No. three dosing pumps to described secondary response pond carry sodium hydroxide, described sodium hydroxide
Storage tank carries sodium hydroxide through No. seven dosing pumps to described passivation pool.
Further, in the present invention, step 2) in, in described primary first-order equation pond, reacted suspension enters once
Sedimentation tank, after standing sedimentation, supernatant enters secondary response pond, and bottom precipitation is discharged, and enters a filter pressing pond and sinks
Shallow lake filter pressing, gained filtrate enters secondary response pond together with the supernatant of primary sedimentation basin;
Step 3) in, in described secondary response pond, reacted suspension enters secondary sedimentation tank, after standing sedimentation, on
Clear liquid enters micro-electrolysis reactor, and bottom precipitation is discharged, and enters secondary filter pressing pond and carries out precipitating filter pressing, gained filtrate and two
The supernatant of secondary sedimentation tank enters micro-electrolysis reactor together;
Step 5) in, the reacted suspension of described passivation pool enters three sedimentation tanks, and after standing sedimentation, supernatant reaches
Mark discharge, bottom precipitation is discharged, and enters three filter pressing ponds and carries out precipitating filter pressing, gained filtrate and the supernatant of three sedimentation tanks
Liquid qualified discharge together.
Beneficial effect: the present invention, compared with traditional technical scheme, has following improvements:
1, this programme uses sodium hydroxide to improve pH, it is to avoid brings calcium ion into, thus prevents a large amount of calcium precipitation
Produce;
2, this programme achieves the recovery of iron phosphate of higher quality, and it can be used for manufacturing iron lithium phosphate electrode material, with
Time evaded the phosphate radical interference effect to subsequent technique;
3, this programme achieves the recycling of aluminium hydroxide, and it can be former as the basis of aluminum electrolysis industry, fire retardant etc.
Material, has evaded aluminium ion and hydroxide thereof the interference effect to subsequent technique simultaneously;
4, the mud that this programme finally produces is mainly ferrite, its Stability Analysis of Structures, is insoluble in acid-alkali salt, dirty without secondary
Dye;Dehydration property is good, it is easy to separate;Having magnetic, recoverable is to other industry;
5, each stock waste water is converged process by this programme, decreases equipment investment and floor space;
6, use micro-electrolysis method reduction chromate, both provided a large amount of source of iron for ensuing ferrite process, and greatly reduced
Conventional ferrite process needs the ferrous sulfate amount added, can also remove present in waste water simultaneously some Organic substances and its
His hard-degraded substance.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
In figure: 1 is an online pH meter, 2 is a blender, and 3 is No. two online pH meters, and 4 is No. two stirrings
Machine, 5 be No. three online pH meters 3,6 be an online ORP meter, 7 is Aeration fan, and 8 is No. four online pH meters,
9 is No. two online ORP meters, and 10 is No. three blenders, and 11 is regulating reservoir, and 12 is primary first-order equation pond, and 13 for once to sink
Pond, shallow lake, 14 is secondary response pond, and 15 is secondary sedimentation tank, and 16 is micro-electrolysis reactor, and 17 is passivation pool, and 18 are
Three sedimentation tanks, 19 is iron sulfate storage tank, and 20 is ferrous sulfate storage tank, and 21 is CSE agent storage tank, and 22 is hydroxide
Sodium storage tank, 23 is PAM storage tank, and 24 is sulfuric acid storage tank, and 25 is a dosing pump, and 26 is No. two dosing pumps, and 27 are
No. three dosing pumps, 28 is No. seven dosing pumps, and 29 is No. four dosing pumps, and 30 is No. five dosing pumps, and 31 is No. nine dosing pumps,
32 is No. six dosing pumps, and 33 is No. eight dosing pumps, and 34 is a filter pressing pond, and 35 is secondary filter pressing pond, and 36 is three pressures
Filter tank, 37 is a sludge pump, and 38 is No. two sludge pumps, and 39 is No. three sludge pumps.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is further described.
As it is shown in figure 1, a kind of processing method containing heavy metal surface treatment waste water, comprise the following steps:
1) wastewater collection: each stock waste water merges in regulating reservoir 11, forms composite waste, the water quality of regulation composite waste
The water yield, the water quality of composite waste is phosphate≤30000mg/L, aluminum≤350mg/L, chromium≤350mg/L, copper≤350mg/L,
Nickel≤350mg/L;
2) primary first-order equation operation: composite waste enters primary first-order equation pond 12 through acid-proof pump, and iron sulfate storage tank 19 is through a meter
Amount pump 25 adds iron sulfate in primary first-order equation pond 12, and iron sulfate and the phosphate radical in composite waste react generation iron phosphate
Precipitation, arranging the time of staying is 2 hours;Sodium hydroxide storage tank 22 is defeated to primary first-order equation pond 12 through a dosing pump 26
Sending sodium hydroxide, regulation pH value is 1.8-2.0, and in the range of this pH, hydrated ferric oxide. will not separate out, and phosphoric acid iron rule
Separating out the most completely, and settling property is good, precipitation filter pressing can realize being separately separated and reclaiming of phosphate radical, keeps away simultaneously
Exempt from the inhibition that precipitation is converted in follow-up ferrite process by phosphate anion to ferrite;In primary first-order equation pond 12
It is provided with a blender 2 and an online pH meter 1;
In primary first-order equation pond 12, reacted suspension enters primary sedimentation basin 13, and after standing sedimentation, supernatant enters two
Secondary response pond 14, bottom precipitation is discharged, and delivers into a filter pressing pond 34 through a sludge pump 37 and carries out precipitating filter pressing,
Gained filtrate enters secondary response pond 14 together with the supernatant of primary sedimentation basin 13;
3) secondary response operation: sodium hydroxide storage tank 22 carries hydroxide through No. three dosing pumps 27 to secondary response pond 14
Sodium, regulation pH value is 3.2-3.5, and reacts generation aluminum hydroxide precipitation with aluminium ion, and under the conditions of this pH, aluminium ion can
Precipitate completely;Secondary response pond 14 is provided with No. two blenders 4 and No. two online pH meters 3;Arranging the time of staying is
30min;
In secondary response pond 14, reacted suspension enters secondary sedimentation tank 15, and after standing sedimentation, supernatant enters micro-
Electrolysis reactor 16, bottom precipitation is discharged, and delivers into secondary filter pressing pond 35 through No. two sludge pumps 38 and carries out precipitating filter pressing,
Gained filtrate enters micro-electrolysis reactor 16 together with the supernatant of secondary sedimentation tank 15;
Wherein, the polyacrylamide PAM, PAM that add 3~5 ‰ in secondary sedimentation tank 15 are water soluble polymer polymerization
Thing, insoluble in most of organic solvents, has good flocculability, can reduce the frictional resistance between liquid, accelerates
Precipitate and separate;PAM is stored in PAM storage tank 23, PAM storage tank 23 through No. four dosing pumps 29 to secondary sedimentation tank
15 conveying PAM;
4) micro-electrolysis reaction operation: carry out aeration in micro-electrolysis reactor 16, aeration rate is 5L/min, sulfuric acid storage tank
24 carry interpolation sulphuric acid through No. five dosing pumps 30 in micro-electrolysis reactor 16, and regulation pH value is 2.0-3.0, carries out micro-
Cell reaction, is provided with micro-electrolysis stuffing in micro-electrolysis reactor 16, the heavy metal ion in composite waste is reduced;
Arranging the time of staying is 2.0-3.0h, keeps ORP < 300mv;No. three online pH meters it are provided with in micro-electrolysis reactor 16
5, an also online ORP meter 6 mensuration oxidation-reduction potential i.e. ORP value, the observation of ORP value contributes to substantially sentencing
Whether the chromate in disconnected waste water reacts complete, when variation water quality is bigger, need to adjust reaction ginseng in time according to ORP value
Number is to prevent reaction not exclusively;It is additionally provided with Aeration fan 7 and aerating system is provided;
Micro-electrolysis stuffing in micro-electrolysis reactor 16 is from Jiangxi producer, and proportion is 1.1 tons/m3, specific surface area is
1.2m2/ g, voidage is about 65%, each component of micro-electrolysis stuffing respectively Fe:75-85% by mass percentage,
C:10-20%, catalyst: 5%;The reacted suspension of electrolysis reactor 16 enters passivation pool 17;
5) passivation reaction operation: ferrous sulfate storage tank 20 carries interpolation sulphuric acid through No. six dosing pumps 32 in passivation pool 17
Ferrous iron, makes the ratio i.e. T of the amount of material in composite wasteFe: TMReaching 5~8:1, described M is heavy metal ion, bag
Include Cr3+、Ni2+Deng;
Sodium hydroxide storage tank 22 adds sodium hydroxide through No. seven dosing pumps 28 to passivation pool 17 conveying, and regulation pH is extremely
9.5-10.0;
CSE agent storage tank 21 adds the CSE reagent of 1-3ppm through No. eight dosing pumps 33 to passivation pool 17 conveying, stirs 1
Hour, make the heavy metal ion reaction in composite waste form spinel type ferrite precipitation;Wherein, CSE reagent is by river
Su Aiteke Environmental Engineering Design academy company limited provides, and its main component is by catalase, peroxide, de-
Hydroacetic acids etc. become to be grouped into, and its mechanism of action is: at normal temperatures and pressures can by ferrum O compoiste material intermediate such as patina gradually
Oxidation forms constitutionally stable ferrite such as Fe3O4, improve mud densification, realize heavy metal sewage sludge minimizing,
Stabilisation, resource;
Spinel structure belongs to more stable structure, and in this technique, heavy metal ion instead of original part Fe2+And Fe3+?
Position in lattice thus precipitate removal, the sludge stabilization that reaction obtains is strong, is insoluble in acid-alkali salt, it is achieved innoxious;
Ferrum is whether to form ferritic key condition with ratio and the pH value condition of the amount of heavy metal substance, and CSE reagent is steady
Fixed gentle Oxidation is then conducive to the raising of ferrite quality;Passivation pool 17 is provided with No. four online pH meters 8, two
Number online ORP meter 9, No. three blenders 10;Passivation pool 17 keeps ORP < 280mv;
The reacted suspension of passivation pool 17 enters three sedimentation tanks 18, after standing sedimentation, supernatant qualified discharge, the end
Portion's precipitation is discharged, and delivers into three filter pressing ponds 36 through No. three sludge pumps 39 and carries out precipitating filter pressing, gained filtrate and three times
The supernatant of sedimentation tank 18 qualified discharge together;
Wherein, three sedimentation tanks 18 add the PAM of 3~5 ‰, accelerates precipitate and separate, quickly realize solid-liquid separation;PAM
Being stored in PAM storage tank 23, PAM storage tank 23 carries PAM through No. nine dosing pumps 31 to described three sedimentation tanks 18.
Embodiment 1
Jiangsu auto technology company, to the processing method containing heavy metal surface treatment waste water, comprises the following steps:
1) wastewater collection: each stock waste water merges in regulating reservoir 11, forms composite waste, the water quality of regulation composite waste
The water yield, the influent quality of composite waste is as shown in table 1;
Table 1 composite waste influent quality index
Sequence number | Project | Index |
1 | The water yield (m3/d) | 1500 |
2 | COD (CODCr)(mg/l) | <800 |
3 | Biochemical oxygen demand (BOD5)(mg/l) | <250 |
4 | Float (SS) (mg/l) | <500 |
5 | Ammonia nitrogen (NH3-N)(mg/l) | <75 |
6 | Oil (mg/l) | <45 |
7 | Total phosphorus (TP) (mg/l) | <3000 |
8 | pH | 2-4 |
9 | Fluorine (F) (mg/l) | <75 |
10 | Nickel (Ni) (mg/l) | <700 |
11 | Aluminum (Al) (mg/l) | <2000 |
12 | Total chromium (TCr)(mg/l) | <2000 |
13 | Anion surfactant (mg/l) | <40 |
2) primary first-order equation operation: composite waste enters primary first-order equation pond 12 through acid-proof pump, and iron sulfate storage tank 19 is through a meter
Amount pump 25 adds iron sulfate in primary first-order equation pond 12, and iron sulfate and the phosphate radical in composite waste react generation iron phosphate
Precipitation, arranging the time of staying is 2 hours;Sodium hydroxide storage tank 22 is defeated to primary first-order equation pond 12 through a dosing pump 26
Sending sodium hydroxide, regulation pH value is 2.0;Primary first-order equation pond 12 is provided with a blender 2 and an online pH meter 1;
In primary first-order equation pond 12, reacted suspension enters primary sedimentation basin 13, and after standing sedimentation, supernatant enters two
Secondary response pond 14, bottom precipitation is discharged, and enters a filter pressing pond 34 and carries out precipitating filter pressing, gained filtrate and primary sedimentation
The supernatant in pond 13 enters secondary response pond 14 together;
3) secondary response operation: sodium hydroxide storage tank 22 carries hydroxide through No. three dosing pumps 27 to secondary response pond 14
Sodium, regulation pH value is 3.5, and reacts generation aluminum hydroxide precipitation with the aluminium ion in composite waste;Secondary response pond
No. two blenders 4 and No. two online pH meters 3 it are provided with in 14;Arranging the time of staying is 30min.
In secondary response pond 14, reacted suspension enters secondary sedimentation tank 15, and after standing sedimentation, supernatant enters micro-
Electrolysis reactor 16, bottom precipitation is discharged, and enters secondary filter pressing pond 35) carry out precipitating filter pressing, gained filtrate and secondary
The supernatant of sedimentation tank 15 enters micro-electrolysis reactor 16 together;
Wherein, secondary sedimentation tank 15 adds the PAM of 3 ‰, accelerates precipitate and separate;PAM is stored in PAM storage tank
In 23, PAM storage tank 23 carries PAM through No. four dosing pumps 29 to secondary sedimentation tank 15;
4) micro-electrolysis reaction operation: carry out aeration in micro-electrolysis reactor 16, aeration rate is 5L/min, sulfuric acid storage tank
24 carry interpolation sulphuric acid through No. five dosing pumps 30 in micro-electrolysis reactor 16, and regulation pH value is 2.0, carries out micro-electricity
Solve reaction, micro-electrolysis reactor 16 is provided with micro-electrolysis stuffing, the heavy metal ion in composite waste is reduced;
Arranging the time of staying is 2.0h, keeps ORP < 300mv;Be provided with in micro-electrolysis reactor 16 No. three online pH meters 5,
A number online ORP meter 6 and Aeration fan 7;
Micro-electrolysis stuffing in micro-electrolysis reactor 16 is from Jiangxi producer, and proportion is 1.1 tons/m3, specific surface area is
1.2m2/ g, voidage is about 65%, each component of micro-electrolysis stuffing respectively Fe:75-85% by mass percentage,
C:10-20%, catalyst: 5%;The reacted suspension of electrolysis reactor 16 enters passivation pool 17;
5) passivation reaction operation: ferrous sulfate storage tank 20 carries interpolation sulphuric acid through No. six dosing pumps 32 in passivation pool 17
Ferrous iron, makes the ratio i.e. T of the amount of material in composite wasteFe: TMReaching 5:1, described M is heavy metal ion, including Cr3+、
Ni2+Deng;
Sodium hydroxide storage tank 22 adds sodium hydroxide through No. seven dosing pumps 28 to passivation pool 17 conveying, regulates pH to 10.0;
CSE agent storage tank 21 adds the CSE reagent of 3ppm through No. eight dosing pumps 33 to passivation pool 17 conveying, stirs 1
Hour, make the heavy metal ion reaction in composite waste form spinel type ferrite precipitation;
Passivation pool 17 is provided with No. four online pH meters 8, No. two online ORP meters 9, No. three blenders 10;Passivation pool
ORP < 280mv is kept in 17;
The reacted suspension of passivation pool 17 enters three sedimentation tanks 18, after standing sedimentation, supernatant qualified discharge, the end
Portion's precipitation is discharged, and enters three filter pressing ponds 36 and carries out precipitating filter pressing, the supernatant one of gained filtrate and three sedimentation tanks 18
Play qualified discharge;
Wherein, three sedimentation tanks 18 add the PAM of 3 ‰, accelerates precipitate and separate, quickly realize solid-liquid separation;PAM
Being stored in PAM storage tank 23, PAM storage tank 23 carries PAM through No. nine dosing pumps 31 to described three sedimentation tanks 18.
Effluent quality requirement is reached, as shown in table 2 after this PROCESS FOR TREATMENT.
Table 2 effluent quality index
Sequence number | Project | Index |
1 | The water yield (m3/d) | 1500 |
2 | COD (CODCr)(mg/l) | ≤400 |
3 | Biochemical oxygen demand (BOD5)(mg/l) | ≤200 |
4 | Float (SS) (mg/l) | ≤200 |
5 | Ammonia nitrogen (NH3-N)(mg/l) | ≤35 |
6 | Oil (mg/l) | ≤20 |
7 | Total phosphorus (TP) (mg/l) | ≤4 |
8 | pH | 6-9 |
9 | Fluorine (F) (mg/l) | ≤20 |
10 | Nickel (Ni) (mg/l) | ≤0.5 |
11 | Aluminum (Al) (mg/l) | ≤3.0 |
12 | Total chromium (TCr) (mg/l) | ≤0.5 |
13 | Anion surfactant (mg/l) | ≤20 |
Embodiment 2
As it is shown in figure 1, a kind of processing method containing heavy metal surface treatment waste water, comprise the following steps:
1) wastewater collection: each stock waste water merges in regulating reservoir 11, forms composite waste, the water quality of regulation composite waste
The water yield, the water quality of composite waste is phosphate≤30000mg/L, aluminum≤350mg/L, chromium≤350mg/L, copper≤350mg/L,
Nickel≤350mg/L;
2) primary first-order equation operation: composite waste enters primary first-order equation pond 12 through acid-proof pump, and iron sulfate storage tank 19 is through a meter
Amount pump 25 adds iron sulfate in primary first-order equation pond 12, and iron sulfate and the phosphate radical in composite waste react generation iron phosphate
Precipitation, arranging the time of staying is 2 hours;Sodium hydroxide storage tank 22 is defeated to primary first-order equation pond 12 through a dosing pump 26
Sending sodium hydroxide, regulation pH value is 1.8;Primary first-order equation pond 12 is provided with a blender 2 and an online pH meter 1;
In primary first-order equation pond 12, reacted suspension enters primary sedimentation basin 13, and after standing sedimentation, supernatant enters two
Secondary response pond 14, bottom precipitation is discharged, and enters a filter pressing pond 34 and carries out precipitating filter pressing, gained filtrate and primary sedimentation
The supernatant in pond 13 enters secondary response pond 14 together;
3) secondary response operation: sodium hydroxide storage tank 22 carries hydroxide through No. three dosing pumps 27 to secondary response pond 14
Sodium, regulation pH value is 3.2, and reacts generation aluminum hydroxide precipitation with aluminium ion;Secondary response pond 14 is provided with No. two
Blender 4 and No. two online pH meters 3;Arranging the time of staying is 30min.
In secondary response pond 14, reacted suspension enters secondary sedimentation tank 15, and after standing sedimentation, supernatant enters micro-
Electrolysis reactor 16, bottom precipitation is discharged, and enters secondary filter pressing pond 35) carry out precipitating filter pressing, gained filtrate and secondary
The supernatant of sedimentation tank 15 enters micro-electrolysis reactor 16 together;
Wherein, secondary sedimentation tank 15 adds the PAM of 5 ‰, accelerates precipitate and separate;PAM is stored in PAM storage tank
In 23, PAM storage tank 23 carries PAM through No. four dosing pumps 29 to secondary sedimentation tank 15;
4) micro-electrolysis reaction operation: carry out aeration in micro-electrolysis reactor 16, aeration rate is 5L/min, sulfuric acid storage tank
24 carry interpolation sulphuric acid through No. five dosing pumps 30 in micro-electrolysis reactor 16, and regulation pH value is 3.0, carries out micro-electricity
Solve reaction, micro-electrolysis reactor 16 is provided with micro-electrolysis stuffing, the heavy metal ion in composite waste is reduced;
Arranging the time of staying is 3.0h, keeps ORP < 300mv;Be provided with in micro-electrolysis reactor 16 No. three online pH meters 5,
A number online ORP meter 6 and Aeration fan 7;
Micro-electrolysis stuffing in micro-electrolysis reactor 16 is from Jiangxi producer, and proportion is 1.1 tons/m3, specific surface area is
1.2m2/ g, voidage is about 65%, each component of micro-electrolysis stuffing respectively Fe:75-85% by mass percentage,
C:10-20%, catalyst: 5%;The reacted suspension of electrolysis reactor 16 enters passivation pool 17;
5) passivation reaction operation: ferrous sulfate storage tank 20 carries interpolation sulphuric acid through No. six dosing pumps 32 in passivation pool 17
Ferrous iron, makes the ratio i.e. T of the amount of material in composite wasteFe: TMReaching 8:1, described M is heavy metal ion, including Cr3+、
Ni2+Deng;
Sodium hydroxide storage tank 22 adds sodium hydroxide through No. seven dosing pumps 28 to passivation pool 17 conveying, regulates pH to 9.5;
CSE agent storage tank 21 adds the CSE reagent of 1ppm through No. eight dosing pumps 33 to passivation pool 17 conveying, stirs 1
Hour, make the heavy metal ion reaction in composite waste form spinel type ferrite precipitation;
Passivation pool 17 is provided with No. four online pH meters 8, No. two online ORP meters 9, No. three blenders 10;Passivation pool
ORP < 280mv is kept in 17;
The reacted suspension of passivation pool 17 enters three sedimentation tanks 18, after standing sedimentation, supernatant qualified discharge, the end
Portion's precipitation is discharged, and enters three filter pressing ponds 36 and carries out precipitating filter pressing, the supernatant one of gained filtrate and three sedimentation tanks 18
Play qualified discharge;
Wherein, three sedimentation tanks 18 add the PAM of 5 ‰, accelerates precipitate and separate, quickly realize solid-liquid separation;PAM
Being stored in PAM storage tank 23, PAM storage tank 23 carries PAM through No. nine dosing pumps 31 to described three sedimentation tanks 18.
The above is only the preferred embodiment of the present invention, it should be pointed out that: for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (10)
1. the processing method containing heavy metal surface treatment waste water, it is characterised in that: comprise the following steps:
1) wastewater collection: each stock waste water merges in regulating reservoir (11), forms composite waste, regulates described composite waste
Water quality and quantity, the water quality of described composite waste is phosphate≤30000mg/L, aluminum≤350mg/L, chromium≤350mg/L,
Copper≤350mg/L, nickel≤350mg/L;
2) primary first-order equation operation: described composite waste enters primary first-order equation pond (12), described primary first-order equation pond (12)
Middle interpolation iron sulfate, described iron sulfate and the phosphate radical in composite waste react generation iron phosphate precipitation;Described primary first-order equation
Pond (12) is also added with sodium hydroxide, regulates pH;
In described primary first-order equation pond (12), reacted suspension enters primary sedimentation basin (13), after standing sedimentation, on
Clear liquid enters secondary response pond (14), and bottom precipitation is discharged;
3) secondary response operation: add sodium hydroxide in described secondary response pond (14), regulates pH, and and aluminium ion
Reaction generates aluminum hydroxide precipitation;
In described secondary response pond (14), reacted suspension enters secondary sedimentation tank (15), after standing sedimentation, on
Clear liquid enters micro-electrolysis reactor (16), and bottom precipitation is discharged;
4) micro-electrolysis reaction operation: described micro-electrolysis reactor carries out aeration in (16), aeration rate is 5L/min, institute
State and micro-electrolysis reactor (16) adds sulphuric acid, regulate pH, carry out micro-electrolysis reaction, by the huge sum of money in composite waste
Belong to ion to reduce;Described micro-electrolysis reactor (16) reacted suspension enters passivation pool (17);
5) passivation reaction operation: add ferrous sulfate in described passivation pool (17), adds sodium hydroxide regulation pH,
And add CSE reagent, and stirring, make the heavy metal ion reaction in composite waste form spinel type ferrite precipitation,
The composition of described CSE reagent includes hydrogen oxide enzyme, peroxide, dehydroactic acid;
Described passivation pool (17) reacted suspension enters three sedimentation tanks (18), and after standing sedimentation, supernatant reaches
Mark discharge, bottom precipitation is discharged.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 2)
In, described primary first-order equation pond (12) is added sodium hydroxide, regulation pH value is 1.8-2.0;Arranging the time of staying is 2
Hour.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 3)
In, described secondary response pond (14) is added sodium hydroxide, regulation pH value is 3.2-3.5;Arranging the time of staying is 30min.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 4)
In, described micro-electrolysis reactor (16) adds sulphuric acid, regulation pH value is 2.0-3.0.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 4)
In, arranging the time of staying in described micro-electrolysis reactor (16) is 2.0-3.0h, keeps ORP < 300mv.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 4)
In, described micro-electrolysis reactor (16) is provided with micro-electrolysis stuffing, the proportion of described micro-electrolysis stuffing is 1.1 tons/m3,
Specific surface area is 1.2m2/ g, voidage is about 65%, and each component of described micro-electrolysis stuffing is distinguished by mass percentage
For Fe:75-85%, C:10-20%, catalyst: 5%.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: step 5)
In, described passivation pool (17) adds ferrous sulfate, makes the ratio i.e. T of the amount of material in composite wasteFe: TMReach 5~
8:1, described M is heavy metal ion, including Cr3+、Ni2+;Add sodium hydroxide regulation pH to 9.5-10.0, and
Add the CSE reagent of 1-3ppm;Described passivation pool (17) keeps ORP < 280mv.
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: described
Secondary sedimentation tank (15) and three sedimentation tanks (18) add the PAM of 3~5 ‰;Described PAM is stored in PAM storage
In tank (23), PAM storage tank (23) carries PAM through No. four dosing pumps (29) to described secondary sedimentation tank (15),
PAM storage tank (23) carries PAM through No. nine dosing pumps (31) to described three sedimentation tanks (18).
Processing method containing heavy metal surface treatment waste water the most according to claim 1, it is characterised in that: described
The sodium hydroxide added in primary first-order equation pond (12), secondary response pond (14) and described passivation pool (17) is all from hydrogen
Sodium oxide storage tank (22), described sodium hydroxide storage tank (22) through a dosing pump (26) to described primary first-order equation pond (12)
Conveying sodium hydroxide, described sodium hydroxide storage tank (22) through No. three dosing pumps (27) to described secondary response pond (14)
Conveying sodium hydroxide, described sodium hydroxide storage tank (22) carries to described passivation pool (17) through No. seven dosing pumps (28)
Sodium hydroxide.
10., according to the arbitrary described processing method containing heavy metal surface treatment waste water of claim 1 to 9, its feature exists
In: step 2) in, in described primary first-order equation pond (12), reacted suspension enters primary sedimentation basin (13), stands
After sedimentation, supernatant enters secondary response pond (14), and bottom precipitation is discharged, and enters a filter pressing pond (34) and sinks
Shallow lake filter pressing, gained filtrate enters secondary response pond (14) together with the supernatant of primary sedimentation basin (13);
Step 3) in, in described secondary response pond (14), reacted suspension enters secondary sedimentation tank (15), stands
After sedimentation, supernatant enters micro-electrolysis reactor (16), and bottom precipitation is discharged, and enters secondary filter pressing pond (35) and carries out
Precipitation filter pressing, gained filtrate enters micro-electrolysis reactor (16) together with the supernatant of secondary sedimentation tank (15);
Step 5) in, described passivation pool (17) reacted suspension enters three sedimentation tanks (18), after standing sedimentation,
Supernatant qualified discharge, bottom precipitation is discharged, and enters three filter pressing ponds (36) and carries out precipitating filter pressing, gained filtrate and three
The supernatant qualified discharge together of secondary sedimentation tank (18).
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