CN104326602B - A kind of sequence batch (process aluminium section bar is fluorine-containing in producing, the method for nickel acid waste water - Google Patents

A kind of sequence batch (process aluminium section bar is fluorine-containing in producing, the method for nickel acid waste water Download PDF

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CN104326602B
CN104326602B CN201410628811.6A CN201410628811A CN104326602B CN 104326602 B CN104326602 B CN 104326602B CN 201410628811 A CN201410628811 A CN 201410628811A CN 104326602 B CN104326602 B CN 104326602B
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waste water
order reaction
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CN104326602A (en
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赵旭德
张丽莉
艾立
肖文胜
汪瀚
郭建林
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Hubei Polytechnic University
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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
    • C02F1/44—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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
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  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses method that is fluorine-containing in the production of a kind of sequence batch (process aluminium section bar, nickel acid waste water, the inventive method in turn includes the following steps: fluorine-containing, nickel acid waste water are collected in wastewater collection pond by (1); (2) waste water is put into first order reaction groove, add saturated milk of lime clear liquid, the pH of regulates liquid is 9.5 ~ 11.0, stirs 15 ~ 20min; (3) step (2) reacted liquid is inputted in a Microfilter, leach fluorine-containing, nickel body refuse; (4) by filtrate input second order reaction groove obtained for step (3), the pH value adding hydrochloric acid soln regulates liquid is 7.0 ~ 7.5, stirs 15 ~ 20min, then adds calcium chloride solution, stirs 15 ~ 20min; (5) by reacted for second order reaction groove liquid input secondary Microfilter, leach fluorine-containing, aluminium body refuse, gained filtrate reaches the emission regulation in GB8978-1996; The inventive method and device are disposed of sewage, and the time is short, cost is low, operation is simple, and treatment effect is stablized, and body refuse is recycled convenient, has good economic benefit and social benefit.

Description

A kind of sequence batch (process aluminium section bar is fluorine-containing in producing, the method for nickel acid waste water
Technical field
The present invention relates to environmental engineering field of waste water treatment, be specifically related to a kind of sequence batch (process aluminium section bar produce in the method for fluorine-containing, nickel acid waste water, have reference value to the wastewater treatment of the heavy metal ion such as fluorine-containing, nickel.
Background technology
China is aluminium section bar big producing country, and aluminium shape surface process comprises rare H 2sO 4degreasing, NH 4hF 2acid etching, NaOH alkaline etching, rare H 2sO 4neutralization, NiSO 4and SnSO 4painted, NiF 2the multiple working procedures such as sealing of hole, every procedure includes reaction and cleaning two portions, and produce a large amount of Cleaning Wastewater thus, this Cleaning Wastewater water quality is as follows: pH value is 3.0 ~ 4.0, F -concentration is 100 ~ 300mgL -1, Ni 2+concentration is 2.0 ~ 3.0mgL -1, Sn 2+concentration is 1.0 ~ 1.5mgL -1, NH 4 +concentration is 2.0 ~ 3.0mgL -1, SO 4 2-concentration is 0.9 ~ 1.1mgL -1, Al 3+concentration is 1.5 ~ 2.5mgL -1, according to the regulation in GB8978-1996 " integrated wastewater discharge standard ", this waste water belongs to the acid waste water that fluorochemical and total nickel concentration value exceed standard, and the pH value in this waste water, fluorochemical belong to Equations of The Second Kind pollutent, F after process -concentration answers≤10mgL -1, pH should in 6 ~ 9 scopes, and nickel is first kind pollutent, and the total nickel of its highest permission emission concentration answers≤1.0mgL -1.
In aluminium section bar factory effluent, the removal of fluorine, nickel generally adopts Ca (OH) 2, CaCO 3, CaO as precipitation agent, but primary sedimentation and secondary sedimentation process all can not make water outlet fluorinion concentration be down to 10mgL -1following emission request, the waste water thus after precipitation process generally adopts and flocculates or adsorb two sections of defluorinating process of combining.According to the literature, existing fluoride wastewater treatment technique and aluminium section bar to containing heavy metal in non-aluminium section bar industry is fluorine-containing in producing, nickel-containing wastewater treatment technology is as follows:
1, non-aluminium section bar industry technique that is fluorine-containing and heavy metal containing wastewater treatment has: 1. Zhao Wei (pollution prevention technique, 1996,9(1), P53 ~ 54) adopt magnesium, living polymer compound MCA water purification agent Coagulation and Adsorption process that calcium, aluminium are principal constituent; 2. Zhang Xuehong (Chinese water supply and drainage, 2006,22(8), P35 ~ 37) and 3. Zhu Yi (rare metal, 2005,29(3), P325 ~ 327) adopt milk of lime precipitation and PAM flocculation combination treatment; 4. Zhou Fen (environmental engineering journal, 2012,6(2), P445 ~ 450) adopt and adjust pH value, CaCl 2precipitation and PAC, PAM flocculation combination treatment.
2, aluminium section bar fluoride wastewater treatment technique has: 1. Tang Wei (Treatment of Industrial Water, 2000,20(10), P19 ~ 20) adopt Ca (OH) 2do precipitation agent, do flocculation agent coupling process with PAC, FW complexing auxiliary agent; 2. Zhang Zhijie (nonmetalliferous ore, 2008,31(5), P59 ~ 61) adopt calcium chloride modified zeolite adsorption treatment; 3. Zhang Zhijie (Treatment of Industrial Water, 2010,30(2), P76 ~ 78) adopt and add Tai-Ace S 150, carbide slag and PAM coagulating kinetics.The removal of nickel in waste water is not all considered in the treatment process of above-mentioned waste water.
3, aluminium section bar nickel-containing wastewater treatment technology has: Wei Xiaoxing (non-ferrous metal chemical industry, 2006,33(2), P75 ~ 77) adopt and adjust after PH, add flocculation agent coagulating kinetics.The removal of fluorine is not considered in above-mentioned treatment process.
4, aluminium section bar is fluorine-containing, nickel waste water treatment process has: 1. Liu Hong (Treatment of Industrial Water, 2008, 28(6), P79 ~ 81), 2. Qi Hao literary composition (Chinese water supply and drainage, 2000, 16(11), P42 ~ 43), 3. the Chen Xiao tinkling of pieces of jade (Yunnan Environmental science, 2003, Z1, P143 ~ 144), 4. Liu Xue (water technology, 2013, 39(1), P132 ~ 135), 5. Jiang Shan (guizhou chemical industry, 2012, 37(2), P36 ~ 38), 6. Li Ping (Treatment of Industrial Water, 2012, 32(11), 62 ~ 64), 7. Jiang Shan (guizhou chemical industry, 2012, 37(2), P36 ~ 38), all adopt to adjust pH value in above-mentioned treatment process, add polyacrylamide (PAM) or be polymerized dimerization aluminium (PAC) and carry out coagulation as flocculation agent, redeposition filters or air-flotation process.
All there is following problem in above-mentioned treatment process that is fluorine-containing, nickel waste water:
1. the use of flocculation agent makes sludge quantity increase, flocculant dosage kind that is too much or very few and flocculation agent all can produce a very large impact flocculating effect, aluminum section industrial wastewater variation water quality is comparatively large, causes treatment effect extremely unstable, often needs to carry out secondary treatment.
2. absorption method is simple to operate, defluorination effect good, the treatment time is short, but the impact of the adsorptive capacity of defluorination effect sorbent suspension, the pH value of fluoride waste and impurities in water is larger, it is not high that value recycled by sorbent material, there is fluorine-containing, that nickel sorbent treatment difficulty is large problem.
3. fluorine-containing sludge as important raw material in chemical industry, metallurgical process by widespread demand, it often adopts on chemical industry heats volatilization to manufacture hydrofluoric acid in acid solution, then with it for raw material manufactures organic and inorganic fluorine cpd.In wastewater treatment process, the use of flocculation agent makes sludge quantity increase, and precipitating sludge composition is also more complicated, and especially organic floculant (as: PAM) and hydrofluoric acid volatilize simultaneously, affect the Treatment for Reuse of fluorine in mud.Fluorine-containing sludge is often discarded by as waste residue, and mud can not get appropriate disposal, causes secondary pollution.
4. nickel-containing sludge belongs to dangerous solid waste, and after using flocculation agent, sludge quantity increases, and in mud, nickel content declines, and make nickel-containing sludge recycle value and reduce, mud recycling difficulty is large.
Summary of the invention
Object of the present invention is exactly generally adopt additional flocculating agents or sorbent material to process for fluorine-containing, nickel waste water at present, fluorine-containing, nickel sludge quantity is caused to be multiplied, and effective constituent reduces in mud, reclaim difficulty, cause the problem of secondary pollution, simultaneously also there is treatment effect extremely unstable in above-mentioned treatment process, is subject to the problem of waste water quality influence of fluctuations, the method for fluorine-containing in providing a kind of sequence batch (process aluminium section bar to produce, nickel acid waste water and device.
A kind of sequence batch (process aluminium section bar of the present invention is fluorine-containing in producing, the method for nickel acid waste water, in turn includes the following steps:
(1) fluorine-containing, the nickel acid waste water that produce in aluminium section bar production process are introduced in wastewater collection pond, the pH value of this waste water is 3.0 ~ 4.0, wherein F -concentration is 100 ~ 300mg/L, Ni 2+concentration is 2.0 ~ 3.0mg/L, Sn 2+concentration is 1.0 ~ 1.5mg/L, NH 4 +concentration is 2.0 ~ 3.0mg/L, SO 4 2-concentration is 0.9 ~ 1.1mg/L, Al 3+concentration is 1.5 ~ 2.5mg/L;
(2) by the first order reaction groove of above-mentioned waste water input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device, under agitation add saturated milk of lime clear liquid, the pH regulating waste water is 9.5 ~ 11.0, stir 15 ~ 20 minutes, the add-on of described waste water is controlled by liquid level on-line monitoring device, and the add-on of described saturated milk of lime clear liquid is controlled by pH on-line monitoring device;
(3) waste water reacted in first order reaction groove is inputted in a Microfilter, waste water is made to be the strainer filtering of 30-50 μm by aperture, in gained filtrate, nickel ion concentration is 0.02 ~ 0.05mg/L, and fluorinion concentration is 45 ~ 50mg/L, and filter residue is recycled as the nickeliferous industrial chemicals of higher-grade;
(4) by the second order reaction groove of filtrate input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device obtained in a Microfilter, under agitation add the hydrochloric acid that massfraction is 8% ~ 10%, the pH regulating filtrate is 7.0 ~ 7.5, stir 15 ~ 20 minutes, add the calcium chloride solution that massfraction is 20 ~ 25% again, add-on is 10 ~ 12ml/L, stir 15 ~ 20 minutes, the add-on of described hydrochloric acid is controlled by pH on-line monitoring device, and the add-on of described calcium chloride is controlled by liquid level on-line monitoring device;
(5) by reacted liquid input secondary Microfilter in second order reaction groove, make liquid passage aperture be the strainer filtering of 30-50 μm, the pH of gained filtrate is 7.0 ~ 7.5, wherein, and F -ionic concn is 2 ~ 6mg/L, and total nickel is 0.02 ~ 0.025mg/L, meets the emission regulation in GB8978-1996, both can be used as water of productive use reuse, can directly discharge again; Gained filter residue utilizes as the low fluorine of heavy metal content, aluminum chemical industry raw materials recovery;
Regulate the pH of waste water to be preferably 10.0 ~ 10.2 in described step (2), churning time is 20min.
The aperture of filter screen of a described Microfilter is preferably 35 μm, and the aperture of filter screen of secondary Microfilter is preferably 50 μm.
A kind of sequence batch (process aluminium section bar of the present invention is fluorine-containing in producing, the device of the method for nickel acid waste water, there is wastewater collection pond, first order reaction groove, Microfilter, second order reaction groove and a secondary Microfilter is in series with successively behind described wastewater collection pond, described wastewater collection pond is positioned at above first order reaction groove, first order reaction groove is connected with the water inlet pipe of secondary Microfilter with a Microfilter respectively with the rising pipe of second order reaction groove, and the residue outlet of a Microfilter and secondary Microfilter extends above a micro-filtration storage mud groove and secondary micro-filtration storage mud groove respectively, described first order reaction groove and second order reaction groove are all equipped with whipping appts, saturated milk of lime clear liquid storage tank is provided with above first order reaction groove, calcium chloride solution storage tank and hydrochloric acid soln storage tank is provided with above second order reaction groove, described wastewater collection pond, saturated milk of lime clear liquid storage tank, calcium chloride solution storage tank, all drain pipe is housed below hydrochloric acid soln storage tank, drain pipe is all equipped with magnetic valve and under meter, magnetic valve on the drain pipe of wherein wastewater collection pond and calcium chloride solution storage tank respectively with a liquid level on-line monitoring device control linkage, the measuring head of liquid level on-line monitoring device stretches in reactive tank, magnetic valve on the drain pipe of saturated milk of lime clear liquid storage tank and hydrochloric acid soln storage tank respectively with a pH on-line monitoring device control linkage, the measuring head of pH on-line monitoring device stretches in reactive tank.
Preferably, in apparatus of the present invention, also have additional a Controlling System, described Controlling System respectively with liquid level on-line monitoring device and the pH on-line monitoring device control linkage of first order reaction groove, second order reaction groove.Such design can reach the omnidistance on-line checkingi of running condition, the volume of waste water in first order reaction groove, second order reaction groove and pH value are carried out on-line checkingi, input operation process programming system, be converted to the control signal of corresponding electromagnetic valve switch, valvular switch is run all under control of the control system, and wastewater treatment process can realize whole-course automation and control.
The principle of the invention is as follows:
(1) in first order reaction groove based on except nickel, make nickel ion concentration up to standard, fluorine is removed by precipitation, throwing out part simultaneously, the fluorinion concentration in waste water is made to be stabilized in 45 ~ 50mg/L under pH is the condition of 9.5 ~ 11.0, reach equilibrium state, in the process, main generation is reacted as follows: a.F -with Ca 2+reaction generates CaF 2precipitation, Ni 2+with OH -reaction generates Ni (OH) 2precipitation, Sn 2+with OH -reaction generates Sn (OH) 2precipitation; B. raise with pH value, Al 3+hydrolysis generates various positively charged hydroxyl complex ion as Al 7(OH) 17 4+, Al 13(OH) 34 5+, Al 13o 4(OH) 24 7+deng the F in, hydroxyl complex ion and waste water -, SO 4 2-attract etc. electronegative Ion Phase, then form positively charged multinuclear aggregate and CaF carried secretly by colloid 2particle, Sn (OH) 2particle and Ni (OH) 2particle forms flco jointly;
Chemical equation is as follows:
2F -+Ca 2+→CaF 2↓；
Ni 2++2OH -→Ni(OH) 2↓；
Sn 2++2OH -→Sn(OH) 2↓
7Al 3++17OH -→Al 7(OH) 17 4+；
Al 7(OH) 17 4++nF -→Al 7(OH) 17-nF n 4+↓+nOH -；
Al 7(OH) 17 4++mSO 4 2-→Al 7(OH) 17-2m(SO 4) m 4+↓+2mOH -
13Al 3++34OH -→Al 13(OH) 34 5+；
Al 13(OH) 34 5++xF -→Al 13(OH) 34-xF x 5+↓+xOH -；
Al 13(OH) 34 5++ySO 4 2-→Al 13(OH) 34-2y(SO 4) y 5+↓+2yOH -；
Al 13O 4(OH) 24 7++zF -→Al 13O 4(OH) 24-zF z 7+↓+zOH -；
……
CaF carried secretly by above-mentioned positively charged multinuclear aggregate and colloid 2particle, Ni (OH) 2particle and Sn (OH) 2particle forms flco throw out jointly; Waste water in first order reaction groove, after above-mentioned reaction, inputs in a Microfilter and filters, the flco formed in removing waste water and throw out, Ni in gained filtrate 2+concentration is 0.02 ~ 0.05mg/L, reaches emission request, F -concentration stabilize is at 40 ~ 45mg/L;
(2) in second order reaction groove, make fluorinion concentration up to standard: by adding pH to 7.0 ~ 7.5 of hydrochloric acid readjustment filtrate in filtrate, improve the positive valence state of micelle in water body, reduce the electrostatic repulsion between micelle, impel between micelle and condensed by compression double electric layer effect, add calcium chloride solution again, part fluorion and calcium ion can be made to react generation calcium fluoride precipitate, pass through absorption charge neutrality effect between micelle simultaneously, the net effect of catching waits the fluorion in water body, calcium fluoride precipitate adsorbs, wrap and remove by filtering during secondary Microfilter in flco, F in gained filtrate -concentration is 2 ~ 6mg/L, Ni 2+concentration is 0.02 ~ 0.025mg/L, and filtrate pH is 7.0 ~ 7.5, lower than the emission regulation (F in GB8978-1996 -concentration answers≤10mgL -1, pH should in 6 ~ 9 scopes, and total nickel answers≤1.0mgL -1).
The present invention compared with prior art, has following characteristics:
(1) in treating processes milk of lime and hydrochloric acid dosage in adopt PH on-line monitoring device to control, calcium chloride adopts and by volume quantitatively adds, added amount of chemical controls simple, accurate, easy to operate, can realize wastewater treatment process whole-course automation after setting up general control system, and treatment effect is stablized.
(2) micro-filtrations are removed in water after flco, adjust back pH by acid adding, add calcium salt method and impel surplus materials in filtrate to produce CaF 2secondary sedimentation and secondary flocculation, decrease the usage quantity of medicament to the full extent.
(3) in sludge handling process, throw out granularity is little, and when not adding flocculation agent, precipitation process needs more than 2 hours, and more muddy.Adopt Microfilter to carry out solid-liquid separation, one batch of wastewater treatment time whole process only needs 1 hours, and the treatment time is short, and body refuse is separated fully, and processed waste water is limpid, more stable than intermediate processing operating performance, can direct reuse after process.
(4) in treating processes without flocculation agent, sorbent material etc. affect mud recycle material add, sludge output is low, is conducive to the recycling of fluorine in mud.
(5) Ni is contained in treating processes 2+, Al 3+collect separately Deng valuable metal ions throw out, improve the recovery value of sludge containing heavy metal.
(6) mud all directly can reclaim comprehensive utilization as industrial chemicals, and the fluorine avoided, the secondary pollution of nickel, can produce good economic benefit and social benefit.
(7) technique is simple, and treatment facility construction cost is low.
(8) process institute's with medicament and be common low value medicine, adding less, reagent cost is about and adds 50% of PAM flocculation sediment treatment process.
The inventive method treatment time is short, and cost is low, and run simple, treatment effect is stablized, and body refuse is recycled convenient, can realize wastewater treatment whole-course automation and control, have good economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
Fig. 2 is the connection diagram of apparatus of the present invention;
Fig. 3 is the control system block diagram of apparatus of the present invention.
In figure: 1-wastewater collection pond, 2-first order reaction groove, 3-Microfilter, 4-second order reaction groove, 5-secondary Microfilter, 6,7-drain pipe, 8,9-residue outlet, 10-micro-filtration storage mud groove, 11-secondary micro-filtration storage mud groove, 12-whipping appts, 13-saturated milk of lime clear liquid storage tank, 14-calcium chloride solution storage tank, 15-hydrochloric acid soln storage tank, 16-chemical feed pipe, 17-magnetic valve, 18-under meter, 19-liquid level on-line measurement device, 20-level gauging head, 21-pH on-line monitoring device, 22-pH measuring head, 23-Controlling System.
Embodiment
Embodiment 1
See Fig. 1, Fig. 2, a kind of sequence batch (process aluminium section bar is fluorine-containing in producing, the method for nickel acid waste water, in turn includes the following steps:
(1) fluorine-containing, the nickel acid waste water that produce in aluminium section bar production process are introduced in wastewater collection pond 1, the pH value of this waste water is 3.5, wherein F -concentration is 253mg/L, Ni 2+concentration is 3.0mg/L, Sn 2+concentration is 1.0mg/L, NH 4 +concentration is 2.0mg/L, SO 4 2-concentration is 1.1mg/L, Al 3+concentration is 1.5mg/L;
(2) by the first order reaction groove 2 of above-mentioned fluorine-containing, nickel acid waste water input tape whipping appts 12, liquid level on-line monitoring device 19 and pH on-line monitoring device 21, open whipping appts, saturated milk of lime clear liquid is added under stirring, the pH regulating waste water is 10.0 ~ 10.2, stir 20 minutes, the add-on of described waste water is controlled by liquid level on-line monitoring device, and the add-on of described saturated milk of lime clear liquid is controlled by pH on-line monitoring device, and the rotating speed of described whipping appts is 200r/min;
(3) waste water reacted in first order reaction groove is inputted in a Microfilter 3, waste water is made to be the strainer filtering of 35 μm by aperture, in filtrate after this step process, nickel ion concentration is 0.03mg/L, fluorinion concentration is 45mg/L, and filter residue enters in a micro-filtration storage mud groove 10 and recycles as the nickeliferous industrial chemicals of higher-grade;
(4) by the second order reaction groove 4 of filtrate input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device obtained in a Microfilter, open whipping appts, add the hydrochloric acid that massfraction is 10%, the pH regulating filtrate is 7.0 ~ 7.2, stir 15 minutes, add the calcium chloride solution that massfraction is 25% again, add-on is 10ml/L, stir 20 minutes, the add-on of described hydrochloric acid is controlled by pH on-line monitoring device, the add-on of described calcium chloride is controlled by liquid level on-line monitoring device, and the rotating speed of described whipping appts is 200r/min;
(5) by reacted liquid input secondary Microfilter 5 in second order reaction groove, make liquid passage aperture be the strainer filtering of 50 μm, the pH of gained filtrate is 7.1, wherein, and F -ionic concn is 2.0mg/L, and total nickel is 0.02mg/L, meets the emission regulation in GB8978-1996, both can be used as water of productive use reuse, can directly discharge again; Gained filter residue enters fluorine low as heavy metal content in secondary micro-filtration storage mud groove 11, aluminum chemical industry raw materials recovery utilizes.
Find through actual production, under the present embodiment processing condition, the effluent quality of waste water is optimum.
Embodiment 2
Sequence batch (process aluminium section bar is fluorine-containing in producing, a method for nickel acid waste water, in turn includes the following steps:
(1) fluorine-containing, the nickel acid waste water that produce in aluminium section bar production process are introduced in wastewater collection pond, the pH value of this waste water is 3.0, wherein F -concentration is 100mg/L, Ni 2+concentration is 2.0mg/L, Sn 2+concentration is 1.5mg/L, NH 4 +concentration is 3.0mg/L, SO 4 2-concentration is 0.9mg/L, Al 3+concentration is 1.5mg/L;
(2) by the first order reaction groove of above-mentioned fluorine-containing, nickel acid waste water input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device, under agitation add saturated milk of lime clear liquid, the pH regulating waste water is 9.5 ~ 10.0, stir 15 minutes, the add-on of described waste water is controlled by liquid level on-line monitoring device, the add-on of described saturated milk of lime clear liquid is controlled by pH on-line monitoring device, and the rotating speed of described whipping appts is 200r/min;
(3) waste water reacted in first order reaction groove is inputted in a Microfilter, waste water is made to be the strainer filtering of 30 μm by aperture, in filtrate after this step process, nickel ion concentration is 0.05mg/L, and fluorinion concentration is 50mg/L, and filter residue is recycled as the nickeliferous industrial chemicals of higher-grade;
(4) by the second order reaction groove of filtrate input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device obtained in a Microfilter, under agitation add the hydrochloric acid that massfraction is 8%, the pH regulating filtrate is 7.3 ~ 7.5, stir 20 minutes, then in second order reaction groove, the calcium chloride solution that massfraction is 20% is added, add-on is 12ml/L, stir 15 minutes, the add-on of described hydrochloric acid is controlled by pH on-line monitoring device, the add-on of described calcium chloride is controlled by liquid level on-line monitoring device, and the rotating speed of described whipping appts is 200r/min;
(5) by reacted liquid input secondary Microfilter in second order reaction groove, make liquid passage aperture be the strainer filtering of 40 μm, the pH of gained filtrate is 7.3, wherein, and F -ionic concn is 6mg/L, and total nickel is 0.05mg/L, meets the emission regulation in GB8978-1996, both can be used as water of productive use reuse, can directly discharge again; Gained filter residue utilizes as the low fluorine of heavy metal content, aluminum chemical industry raw materials recovery.
Embodiment 3
Sequence batch (process aluminium section bar is fluorine-containing in producing, a method for nickel acid waste water, in turn includes the following steps:
(1) fluorine-containing, the nickel acid waste water that produce in aluminium section bar production process are introduced in wastewater collection pond, the pH value of this waste water is 4.0, wherein F -concentration is 300mg/L, Ni 2+concentration is 2.5mg/L, Sn 2+concentration is 1.2mg/L, NH 4 +concentration is 2.5mg/L, SO 4 2-concentration is 1.0mg/L, Al 3+concentration is 2.0mg/L;
(2) by the first order reaction groove of above-mentioned fluorine-containing, nickel acid waste water input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device, open whipping appts, and in first order reaction groove, add saturated milk of lime clear liquid, the pH regulating waste water is 10.6 ~ 11.0, stir 20 minutes, the add-on of described waste water is controlled by liquid level on-line monitoring device, and the add-on of described saturated milk of lime clear liquid is controlled by pH on-line monitoring device, and the rotating speed of described whipping appts is 200r/min;
(3) waste water reacted in first order reaction groove is inputted in a Microfilter, waste water is made to be the strainer filtering of 40 μm by aperture, in filtrate after this step process, nickel ion concentration is 0.04mg/L, and fluorinion concentration is 48mg/L, and filter residue is recycled as the nickeliferous industrial chemicals of higher-grade;
(4) by filtrate input tape whipping appts obtained in a Microfilter, in the second order reaction groove of liquid level on-line monitoring device and pH on-line monitoring device, open whipping appts, and the hydrochloric acid that massfraction is 9% is added in second order reaction groove, the pH regulating filtrate is 7.2 ~ 7.4, stir 15 minutes, then in second order reaction groove, the calcium chloride solution that massfraction is 23% is added, add-on is 11ml/L, stir 20 minutes, the add-on of described hydrochloric acid is controlled by pH on-line monitoring device, the add-on of described calcium chloride solution is controlled by liquid level on-line monitoring device, the rotating speed of described whipping appts is 200r/min,
(5) by reacted liquid input secondary Microfilter in second order reaction groove, make liquid passage aperture be the strainer filtering of 30 μm, the pH of gained filtrate is 7.3, wherein, and F -ionic concn is 4.6mg/L, and total nickel is 0.035mg/L, meets the emission regulation in GB8978-1996, both can be used as water of productive use reuse, can directly discharge again; Gained filter residue utilizes as the low fluorine of heavy metal content, aluminum chemical industry raw materials recovery.
Embodiment 4
See Fig. 2, a kind of sequence batch (process aluminium section bar is fluorine-containing in producing, the device of the method for nickel acid waste water, there is wastewater collection 1, first order reaction groove 2 is in series with successively behind described wastewater collection pond, a Microfilter 3, second order reaction groove 4 and secondary Microfilter 5, described wastewater collection pond is positioned at above first order reaction groove, first order reaction groove is connected with the water inlet pipe of secondary Microfilter with a Microfilter with 7 respectively with the rising pipe 6 of second order reaction groove, the residue outlet 8 and 9 of a Microfilter and secondary Microfilter extends above a micro-filtration storage mud groove 10 and secondary micro-filtration storage mud groove 11 respectively, described first order reaction groove and second order reaction groove are all equipped with whipping appts 12, saturated milk of lime clear liquid storage tank 13 is provided with above first order reaction groove, calcium chloride solution storage tank 14 and hydrochloric acid soln storage tank 15 is provided with above second order reaction groove, described wastewater collection pond, saturated milk of lime clear liquid storage tank, calcium chloride solution storage tank, below hydrochloric acid soln storage tank, drain pipe 16 is all housed, magnetic valve 17 and under meter 18 drain pipe be all equipped with, magnetic valve on the drain pipe of wherein wastewater collection pond 1 and calcium chloride solution storage tank 14 respectively with liquid level on-line monitoring device 19 control linkage, the measuring head 20 of liquid level on-line monitoring device stretches in reactive tank, magnetic valve on the drain pipe of saturated milk of lime clear liquid storage tank 13 and hydrochloric acid soln storage tank 15 respectively with pH on-line monitoring device 21 control linkage, the measuring head 22 of pH on-line monitoring device stretches in reactive tank.
See Fig. 3, a Controlling System 23 in apparatus of the present invention, can also be set up, described Controlling System 23 respectively with liquid level on-line monitoring device 19 and pH on-line monitoring device 21 control linkage of first order reaction groove 2, second order reaction groove 4.Such design can reach the full on-line checkingi of running condition, the volume of waste water in first order reaction groove, second order reaction groove and pH value are carried out on-line checkingi, input operation process programming system, be converted to the control signal of corresponding electromagnetic valve switch, valvular switch is run all under control of the control system, and wastewater treatment process can realize whole-course automation and control.

Claims (4)

1. sequence batch (process aluminium section bar produce in the method for fluorine-containing, nickel acid waste water, it is characterized in that in turn including the following steps:
(1) fluorine-containing, the nickel acid waste water that produce in aluminium section bar production process are introduced in wastewater collection pond, the pH value of this waste water is 3.0 ~ 4.0, wherein F -concentration is 100 ~ 300mg/L, Ni 2+concentration is 2.0 ~ 3.0mg/L, Sn 2+concentration is 1.0 ~ 1.5mg/L, NH 4 +concentration is 2.0 ~ 3.0mg/L, SO 4 2-concentration is 0.9 ~ 1.1mg/L, Al 3+concentration is 1.5 ~ 2.5mg/L;
(2) by the first order reaction groove of above-mentioned waste water input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device, under agitation add saturated milk of lime clear liquid, the pH regulating waste water is 9.5 ~ 11.0, stir 15 ~ 20 minutes, the add-on of described waste water is controlled by liquid level on-line monitoring device, and the add-on of described saturated milk of lime clear liquid is controlled by pH on-line monitoring device;
(3) waste water reacted in first order reaction groove is inputted in a Microfilter, waste water is made to be the strainer filtering of 30 ~ 50 μm by aperture, in gained filtrate, nickel ion concentration is 0.02 ~ 0.05mg/L, fluorinion concentration is 45 ~ 50mg/L, and filter residue is recycled as the nickeliferous industrial chemicals of higher-grade;
(4) by the second order reaction groove of filtrate input tape whipping appts, liquid level on-line monitoring device and pH on-line monitoring device obtained in a Microfilter, under agitation add the hydrochloric acid that massfraction is 8% ~ 10%, the pH regulating filtrate is 7.0 ~ 7.5, stir 15 ~ 20 minutes, add the calcium chloride solution that massfraction is 20 ~ 25% again, add-on is 10 ~ 12ml/L, stir 15 ~ 20 minutes, the add-on of described hydrochloric acid is controlled by pH on-line monitoring device, and the add-on of described calcium chloride is controlled by liquid level on-line monitoring device;
(5) by reacted liquid input secondary Microfilter in second order reaction groove, make liquid passage aperture be the strainer filtering of 30 ~ 50 μm, the pH of gained filtrate is 7.0 ~ 7.5, wherein, and F -ionic concn is 2 ~ 6mg/L, and total nickel is 0.02 ~ 0.025mg/L, meets the emission regulation in GB8978-1996, both can be used as water of productive use reuse, can directly discharge again; Gained filter residue utilizes as the low fluorine of heavy metal content, aluminum chemical industry raw materials recovery;
The device used in aforesaid method, there is wastewater collection pond, first order reaction groove, Microfilter, second order reaction groove and a secondary Microfilter is in series with successively behind described wastewater collection pond, described wastewater collection pond is positioned at above first order reaction groove, first order reaction groove is connected with the water inlet pipe of secondary Microfilter with a Microfilter respectively with the rising pipe of second order reaction groove, and the residue outlet of a Microfilter and secondary Microfilter extends above a micro-filtration storage mud groove and secondary micro-filtration storage mud groove respectively, described first order reaction groove and second order reaction groove are all equipped with whipping appts, saturated milk of lime clear liquid storage tank is provided with above first order reaction groove, calcium chloride solution storage tank and hydrochloric acid soln storage tank is provided with above second order reaction groove, described wastewater collection pond, saturated milk of lime clear liquid storage tank, calcium chloride solution storage tank, all drain pipe is housed below hydrochloric acid soln storage tank, drain pipe is all equipped with magnetic valve and under meter, magnetic valve on the drain pipe of wherein wastewater collection pond and calcium chloride solution storage tank respectively with a liquid level on-line monitoring device control linkage, the measuring head of liquid level on-line monitoring device stretches in reactive tank, magnetic valve on the drain pipe of saturated milk of lime clear liquid storage tank and hydrochloric acid soln storage tank respectively with a pH on-line monitoring device control linkage, the measuring head of pH on-line monitoring device stretches in reactive tank.
2. the method for fluorine-containing in producing, the nickel acid waste water of a kind of sequence batch (process aluminium section bar according to claim 1, is characterized in that: the pH regulating waste water in step (2) is 10.0 ~ 10.2, and churning time is 20min.
3. the method for fluorine-containing in producing, the nickel acid waste water of a kind of sequence batch (process aluminium section bar according to claim 1, it is characterized in that: the aperture of filter screen of a described Microfilter is 35 μm, the aperture of filter screen of secondary Microfilter is 50 μm.
4. the method for fluorine-containing in producing, the nickel acid waste water of a kind of sequence batch (process aluminium section bar according to claim 1, it is characterized in that: also have additional a Controlling System, described Controlling System respectively with liquid level on-line monitoring device and the pH on-line monitoring device control linkage of first order reaction groove, second order reaction groove.
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