CN100450592C - Metal smelting factory sewage reclaiming method based on membrane filtering technique - Google Patents

Metal smelting factory sewage reclaiming method based on membrane filtering technique Download PDF

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CN100450592C
CN100450592C CNB2007100086426A CN200710008642A CN100450592C CN 100450592 C CN100450592 C CN 100450592C CN B2007100086426 A CNB2007100086426 A CN B2007100086426A CN 200710008642 A CN200710008642 A CN 200710008642A CN 100450592 C CN100450592 C CN 100450592C
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sewage
membrane
water
metal smelting
filters
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CNB2007100086426A
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Chinese (zh)
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CN101041485A (en
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蓝伟光
严滨
王刚
王锦龙
朱振煌
刘久清
方富林
洪昱斌
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三达膜科技(厦门)有限公司
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Abstract

The invention discloses a wastewater recycling method of metal smelting plant based on film filtering technique, which comprises the following steps: providing a improved waste water processing craft of metal smelting plant; adding water disposal coagulator into waste water; forming alum flower; filtering the waste water; removing big particle foreign matter; filtering through fabric filtering element; removing suspended matter and small foreign matter; pumping into ultra filtration system; filtering; removing minute suspended matter, organic matter and bacteria and so on materials; getting ultra filtration dialysate and concentrated liquid; pumping dialysate into sodium filter (or hyperfiltration )system; filtering; removing heavy metal, calcium ion; getting sodium filter (or hyperfiltration) dialysate and concentrated liquid; merging concentrated liquid; storing in water tank; coagulating sedimentation; discharging.

Description

A kind of metal smelting factory sewage reclaiming method based on membrane filtration technique
Technical field
The present invention relates to a kind of sewage disposal, particularly relate to a kind of metal smelting factory sewage regeneration method that adopts membrane filtration technique.
Background technology
Along with the increase of population, the urbanization that the continuous expansion of people's scope of activities and development of industry and agriculture and population are lived, a large amount of industrial production sewage, agricultural production sewage and people's sanitary sewage are discharged into environment, and the pollution problem of water is more and more serious.Water is the base substance basis that people depend on for existence, and China is a country that water resource relatively lacks, and therefore, treated being back to of various trade effluents is produced so that using water wisely is present focus.In all types of industries sewage, the sewage of metal smelt enterprise is owing to industry characteristic, and its content of organics is low, is easy to reuse.But because the characteristics of its sewage treatment process are the coagulant that use lime as sewage disposal more, so calcium ion content is higher in the sewage, generally more than 250mg/L, sometimes even reach 2000mg/L.Because the existence of a large amount of calcium ions causes in reusing sewage very easily fouling in production process, therefore most of metal smelt enterprise all fails reusing sewage in production.Current, for the method for metal smelting factory sewage reclaiming mainly be:
1. decrement method: become recirculated water in order to make waste water, before the inlet pipe road, destroy the height degree of supersaturation of calcium ion in the sewage, can suitably reduce the dosage of milk of lime in the sewage disposal, perhaps use the pH value that other alkaline matters (as caustic soda etc.) come adjustment of acidity waste water instead.But will certainly improve the disposal cost of waste water so greatly, and the possibility of fouling can not be got rid of fully still.This method usually is limited by its economy.
2. physics method: utilize the effect of high-voltage electrostatic field, change the electronic structure in the hydrone, the water dipole surrounds yin, yang ion in the water, and be by positive and negative order that the chain proper alignment makes it can not freely-movable, unlikely trend tube wall of institute's cation and wall in the water, thus stop calcium, magnesium ion to form incrustation scale.Electrostatic-scaling device in the market, electronic descaling device and ionic rod water treater etc. all are based on the product that this principle is made.This method industrialization difficulty is bigger.
3. material modification method: select for use material that the surface can be big as water-supply-pipe, make the calcium ion can't be in the material surface fouling, this method is achieving no breakthrough property progress so far, is the problem that will be worth research from now on.
4. antisludging agent method: add the antisludging agent of efficient low dosage, this method is one of antiscaling method that generally uses at present.The mechanism of action of antisludging agent is:
1) belong to ion with underwater gold and form stable complex compound or the chelate of solubility, thus yin, yang ions binding and fouling in the prevention system;
2) with the polymer of anion or nonionic the suspended particulate that can form dirt is surrounded, make it with enough identical charges, mutually exclusive and lose cementitiousness, make dirt particle stabilized in dispersity;
3) can play the destruction crystal and arrange and make the lattice distortion in order, the effect of generation distortion, crystal grain no longer increases in surface of solids one-tenth dirty, thereby can reach the purpose of controlling dirt deposition.
This method is a common method, but owing to do not remove calcium ion residual in the sewage theoretically, therefore in use, along with the increase of cooling water cycle-index, after calcium ion concentration improves, the possibility that forms fouling is arranged still.
5. ion-exchange: ion-exchange usually with sewage through necessary preliminary treatment (filtering) as flocculation sediment after, pump into ion-exchange unit, through ion-exchange, remove the recirculated water that cation in the running water obtains not having calcium.But this method cost is higher, and under higher calcium concentration, the resin frequent regeneration can produce the new waste water of some, contaminated environment.
Lianyuan Iron and Steel Group Co., Ltd discloses a kind of filter press sewage flocculation device that converter steelmaking process is handled converter sewage that is used in notification number is the utility model patent of CN2712913, the agitator that it mainly is made of container 8 and reductor 4, puddler 7, paddle 5, sewage induction pipe 9, liquid medicine inlet tube 2 etc. are formed.From the converter sewage of sewage induction pipe 9 with enter container 8 after the liquid medicine that contains high polymer coagulant from liquid medicine inlet tube 2 mixes, under the effect of puddler 7 and paddle 5, make converter sewage and high polymer coagulant further mix the flocculation rate of accelerate sludge, enter into filter press 10 through effluent outfall 6, filter press 10 press filtrations with the mud in the sewage and moisture from, mud after the separation becomes mud cake and send next procedure to handle the water recycling after the separation.This device extends to the sewage disposal on electric furnace smelting process or the blast furnace.
Dong Jiawei provides a kind of zero discharge process for treating sewage during smelting process in the application for a patent for invention of publication number for CN1699221, be the improvement through neutralization, oxidation, precipitation of sewage that the flue gas during smelting spray pickling is produced.The steam cooling transformation that the blast furnace drum is discharged is a water, adds supernatant and handles and cause casting slag machine in the water and the external crucible cinder notch is used for cooling casting slag and Water Quenching Slag.Concrete technology is that treated to the sewage that the flue gas during smelting spray pickling is produced, supernatant is handled water and stored; The steam that the blast furnace drum is discharged is water through the heat exchanger cooling transformation, adds supernatant and handles in the water, causes casting slag machine as cooling water, introduces the external crucible cinder notch and is used for the Water Quenching Slag cooling water.Characteristics of the present invention are, smelting process for production and waste water control craft science are designed, organically combine, the sewage that acid cleaning and purification procedure is produced all consumes in smelting production process, realize the production waste zero-emission, the present invention is the pollution treatment new technology that a kind of design science, technology are reasonable, can effectively eradicate smelting sewage.
Practising outstanding peak provides a kind of and handles the method for non-ferrous metal metallurgy waste water with diatomite in the application for a patent for invention of publication number for CN1504426, add diatomite in the waste water that mixes up the pH value, fully stirs and precipitates.Because diatomaceous absorption is very competent, can solve in the traditional handicraft and can't carry out flocculation sediment to small particle and particle, environment is continued to produce the problem of harm, the effect of sewage water treatment method of the present invention is fine, clearance reaches more than 95%, and cost reduces more than 30%.
Summary of the invention
The objective of the invention is to actual environment at present general lack of water, and the existing shortcoming that metal smelt enterprise sewage reclaiming method is existed, a kind of sewage treatment process of metallurgical works of improvement is provided, makes sewage after routine is handled after the film system handles, can be back to the method for production.
Technical scheme of the present invention is: the sewage of metallurgical works is through after the conventional treatment, and the subject matter that influences reuse in the sewage is a large amount of calcium ions of adding in the sewage treatment process, and calcium ion can cause fouling in reuse process subsequently.Adopt membrane technology to hold back calcium ion in the sewage, make the calcium ion of water outlet be lower than 50mg/L, satisfy reuse requirement (with reference to national recirculated cooling water standard in the annex) fully, thereby reduce production costs and and improved water utilization rate.
The present invention includes following steps:
1) coagulation: the sewage of energy qualified discharge after the metallurgical works processing is added water treatment coagulant, make the colloid coagulation in the sewage, form alumen ustum.
2) sand filtration is filtered: the sewage behind the coagulation is filtered by sandfiltration pot, except that impurity such as the oarse-grained solid suspension in the decontaminated water, colloids.
3) fabric filter element filters: will filter by fabric filter element through the sand filtration filtered sewage, and further remove suspension in the water body and less impurity.
4) ultra-filtration filters: will pump into ultrafiltration system through the fabric filter element filtered sewage and filter, and remove materials such as small suspension, organic matter and bacterium, and get ultrafiltration dialysis liquid and concentrate.
5) nanofiltration (or counter-infiltration) is filtered: the dislysate behind ultra-filtration filters is pumped into nanofiltration (or counter-infiltration) system filtration with booster pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration (or counter-infiltration) dislysate and concentrate.
6) processing of concentrate: ultrafiltration and the merging of nanofiltration (or counter-infiltration) gained concentrate are stored in the tank, through the discharging of lime coagulation post precipitation.
In step 1), described water treatment coagulant is selected from aluminium polychloride, polyacrylamide or similar water treatment coagulant.
In step 4), described ultra-filtration filters is to adopt the water pump supercharging, under intake pressure 5~6bar condition, make the sewage that filters through fabric filter element directly by ultrafiltration membrane system filter dislysate and concentrate.It is that molecular cut off is 50000~300000 polysulphone super-filter membrane, poly (ether-sulfone) ultrafiltration membrane, poly-flutolanil milipore filter that described ultrafiltration system filters the milipore filter that is adopted, acetate fiber milipore filter, polyvinylidene fluoride (PVDF) ultrafiltration membrane etc., its condition of work is a normal temperature, entrance pressure: 0.5~0.8MPa, go out to press: 0.35~0.65MPa, pressure differential: 0.1~0.15MPa.
In step 5), it is that molecular cut off is 150~300 polysulfones, polyether sulfone, cellulose acetate or composite nanometer filtering film etc. that described nanofiltration system is filtered selected membrane material, its condition of work is: temperature: normal temperature, entrance pressure: 0.7~4.5MPa, go out to press: 0.6~4.25MPa, pressure differential: 0.1~0.15MPa; Or counter-infiltration system to filter selected membrane material be polysulfones, polyether sulfone, polyamide, cellulose acetate or composite nanometer filtering film etc., its condition of work is: temperature: normal temperature, entrance pressure: 0.7~2MPa goes out to press: 0.6~1.9MPa, pressure differential 0.1~0.15MPa.Add the antisludging agent of 2~5mg/L in the dislysate behind ultra-filtration filters.
Nanofiltration (or counter-infiltration) gained dislysate (water) can merge to be stored in the tank, with pump water is pumped into the water pipe network of cooling circulating water, is back in the production.
In step 6), through the lime coagulation post precipitation, the most handy sulfuric acid is regulated pH to 6~9 back dischargings.
Compare with existing metallurgic sewage treatment technology, the present invention has following outstanding advantage: 1) adopt the membrane technology of combination to handle, can effectively remove suspension, bacterium, macromolecular compound, heavy metal ion and calcium ion in the sewage, make water outlet reach the recirculated cooling water standard (referring to subordinate list: national circulating cooling water quality standard), be back to production.2) adopt film system handles metal smelting factory sewage stable effluent quality.
The specific embodiment
Embodiment 1: the sewage situation of certain smelting lead refinery is referring to table 1.
Table 1
Find out in the former water of sewage by table 1 and to contain contents of many kinds of heavy metal ion, and contain certain calcium ion, after original place science and engineering skill, can reach the sewage drainage standard of national regulation.Behind membrane treatment process of the present invention, satisfy the needs of recirculated cooling water fully.
The step that below provides processing procedure is as follows:
1) coagulation: the sewage with energy qualified discharge after the metallurgical works processing, by adding aluminium polychloride and polyacrylamide (concentration is respectively 100mg/L and 5mg/L), make the colloid coagulation in the sewage, form alumen ustum.
2) sand filtration is filtered: with the sewage behind the coagulation, filter by sandfiltration pot, except that impurity such as the oarse-grained solid suspension in the decontaminated water, colloids.
3) fabric filter element filters: will filter by fabric filter element through the sand filtration filtered sewage, and further remove suspension in the water body and less impurity.
4) ultra-filtration filters: will pump into ultrafiltration system through the fabric filter element filtered sewage and filter.Membrane material is a polyether sulfone, and molecular cut off is 10000.Entrance pressure 0.5MPa goes out to press 0.35MPa.Remove materials such as small suspension, organic matter and bacterium and get ultrafiltration dialysis liquid and concentrate.By the dislysate of control acquisition and the flow-rate ratio of concentrate, the rate of recovery 95% of control ultra-filtration filters.
5) nanofiltration is filtered: the dislysate behind ultra-filtration filters is pumped into the nanofiltration system filtration with booster pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration dislysate and concentrate.Membrane material is a polysulfones, molecular cut off 100.Entrance pressure 1MPa goes out to press 0.85MPa.By the dislysate of control acquisition and the flow-rate ratio of concentrate, the rate of recovery 70% that the control nanofiltration is filtered.In the nanofiltration system running, add the antisludging agent of 2mg/L simultaneously.
The processing of concentrate: ultrafiltration and the merging of nanofiltration gained concentrate are stored in the tank,, regulated pH to 8 back qualified discharge with 20% sulfuric acid through the lime coagulation post precipitation of adding 0.5%.
The utilization of dislysate: nanofiltration gained dislysate merges to be stored in the tank, with pump water is pumped into the water pipe network of cooling circulating water, is back in the production.
Embodiment 2: certain smelts the sewage situation in copper work referring to table 2.
Table 2
Find out in the former water of sewage by table 2 and to contain contents of many kinds of heavy metal ion, and contain higher calcium ion, after original place science and engineering skill, can reach the sewage drainage standard of national regulation.Behind membrane treatment process of the present invention, satisfy the needs of recirculated cooling water fully.
Treatment step is as follows:
1) coagulation: the sewage with energy qualified discharge after the metallurgical works processing, by adding poly-ferric chloride and polyacrylamide (concentration is respectively 70mg/L and 3mg/L), make the colloid coagulation in the sewage, form alumen ustum.
2) sand filtration is filtered: with the sewage behind the coagulation, filter by sandfiltration pot, except that impurity such as the oarse-grained solid suspension in the decontaminated water, colloids.
3) fabric filter element filters: will filter by fabric filter element through the sand filtration filtered sewage, and further remove suspension in the water body and less impurity.
4) ultra-filtration filters: will pump into ultrafiltration system through the fabric filter element filtered sewage and filter.Membrane material is a polytetrafluoroethylene (PTFE), and molecular cut off is 20000.Entrance pressure 0.5MPa goes out to press 0.35MPa.Remove materials such as small suspension, organic matter and bacterium, get ultrafiltration dialysis liquid and concentrate.By the dislysate of control acquisition and the flow-rate ratio of concentrate, the rate of recovery 95% of control ultra-filtration filters.
5) osmosis filtration: the dislysate behind ultra-filtration filters is pumped into the counter-infiltration system filtration with booster pump, remove heavy metal, calcium ion plasma in the water, get counter-infiltration dislysate and concentrate.Membrane material is a cellulose acetate.Entrance pressure 0.7MPa goes out to press 0.6MPa.By the dislysate of control acquisition and the flow-rate ratio of concentrate, the rate of recovery 65% of control osmosis filtration.In the counter-infiltration system running, add the antisludging agent of 3mg/L simultaneously in right amount.
The processing of concentrate: ultrafiltration and the merging of nanofiltration gained concentrate are stored in the tank,, regulated pH to 8 back qualified discharge with 20% sulfuric acid through the lime coagulation post precipitation of adding 0.5%.
The utilization of dislysate: nanofiltration gained dislysate merges to be stored in the tank, with pump water is pumped into the water pipe network of cooling circulating water, is back in the production.
Subordinate list: national circulating cooling water quality standard

Claims (10)

1. the metal smelting factory sewage reclaiming method based on membrane filtration technique is characterized in that comprising the steps:
1) coagulation: the sewage of energy qualified discharge after the metallurgical works processing is added water treatment coagulant, make the colloid coagulation in the sewage, form alumen ustum;
2) sand filtration is filtered: the sewage behind the coagulation is filtered by sandfiltration pot, remove oarse-grained solid suspension and colloidal impurity in the decontaminated water;
3) fabric filter element filters: will filter by fabric filter element through the sand filtration filtered sewage, and further remove suspension in the water body and less impurity;
4) ultra-filtration filters: will pump into ultrafiltration system through the fabric filter element filtered sewage and filter, and remove materials such as small suspension, organic matter and bacterium, and get ultrafiltration dialysis liquid and concentrate;
5) nanofiltration or osmosis filtration: the dislysate behind ultra-filtration filters is pumped into nanofiltration or counter-infiltration system filtration with booster pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration or counter-infiltration dislysate and concentrate;
6) processing of concentrate: ultrafiltration and nanofiltration or counter-infiltration gained concentrate merged store in the tank, through the discharging of lime coagulation post precipitation.
2. a kind of metal smelting factory sewage reclaiming method based on membrane filtration technique as claimed in claim 1 is characterized in that in step 1), described water treatment coagulant is selected from aluminium polychloride or polyacrylamide.
3. a kind of metal smelting factory sewage reclaiming method as claimed in claim 1 based on membrane filtration technique, it is characterized in that in step 4), described ultra-filtration filters is to adopt the water pump supercharging, under intake pressure 0.5~0.6MPa condition, make the sewage that filters through fabric filter element directly by ultrafiltration membrane system filter dislysate and concentrate; It is that molecular cut off is 50000~300000 polysulphone super-filter membrane, poly (ether-sulfone) ultrafiltration membrane, poly-flutolanil milipore filter that described ultrafiltration system filters the milipore filter that is adopted, acetate fiber milipore filter or polyvinylidene fluoride (PVDF) ultrafiltration membrane.
4. a kind of metal smelting factory sewage reclaiming method as claimed in claim 1 based on membrane filtration technique, it is characterized in that in step 4), it is normal temperature that described ultrafiltration system filters the condition of work that is adopted, and go out to press: 0.35~0.65MPa, pressure differential is 0.1~0.15MPa.
5. a kind of metal smelting factory sewage reclaiming method as claimed in claim 1 based on membrane filtration technique, it is characterized in that in step 5) it is that molecular cut off is 150~300 polysulfones, polyether sulfone, cellulose acetate or composite nanometer filtering film that described nanofiltration system is filtered selected membrane material.
6. as claim 1 or 5 described a kind of metal smelting factory sewage reclaiming methods based on membrane filtration technique, it is characterized in that in step 5), described nanofiltration system is filtered selected condition of work: temperature: normal temperature, entrance pressure: 0.7~4.5MPa, go out to press: 0.6~4.25MPa, pressure differential: 0.1~0.15MPa.
7. as claim 1 or 5 described a kind of metal smelting factory sewage reclaiming methods based on membrane filtration technique, it is characterized in that in step 5) it is polysulfones, polyether sulfone, polyamide, cellulose acetate or composite nanometer filtering film that described counter-infiltration system filters selected membrane material.
8. as claim 1 or 5 described a kind of metal smelting factory sewage reclaiming methods based on membrane filtration technique, it is characterized in that in step 5), the condition of work that described counter-infiltration system filters is: temperature: normal temperature, entrance pressure: 0.7~2MPa, go out to press: 0.6~1.9MPa, pressure differential: 0.1~0.15MPa.
9. as claim 1 or 5 described a kind of metal smelting factory sewage reclaiming methods, it is characterized in that in step 5), adding the antisludging agent of 2~5mg/L in the dislysate behind ultra-filtration filters based on membrane filtration technique.
10. a kind of metal smelting factory sewage reclaiming method based on membrane filtration technique as claimed in claim 1 is characterized in that in step 6), through the lime coagulation post precipitation, regulates pH to 6~9 back dischargings with sulfuric acid.
CNB2007100086426A 2007-02-15 2007-02-15 Metal smelting factory sewage reclaiming method based on membrane filtering technique CN100450592C (en)

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