CN101041485A - 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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Publication number
CN101041485A
CN101041485A CN 200710008642 CN200710008642A CN101041485A CN 101041485 A CN101041485 A CN 101041485A CN 200710008642 CN200710008642 CN 200710008642 CN 200710008642 A CN200710008642 A CN 200710008642A CN 101041485 A CN101041485 A CN 101041485A
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sewage
filtration
membrane
water
metal smelting
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CN100450592C (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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Suntar Membrane Technology Xiamen Co Ltd
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Suntar Membrane Technology Xiamen Co Ltd
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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 activity and development of industry and agriculture and population are lived, a large amount of industrial production sewage, agriculture 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 resources relatively lacks, and therefore, treated being back to of various industrial sewages is produced so that water saving is present focus.In all types of industries sewage, the sewage of Metal smelting enterprise is owing to industry characteristic, and its organic content is low, is easy to reuse.But because the characteristics of its sewage treatment process are the coagulating agent 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 smelting 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 processing costs 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 tension electrostatic field, change the electronic structure in the water molecules, 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 free movement, 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 the big material of surface energy as hydraulic 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. Scale inhibitors method: add the Scale inhibitors of efficient low dosage, this method is one of antiscaling method that generally uses at present.The mechanism of action of Scale inhibitors is:
1) belong to ion with underwater gold and form stable complex compound or the chelate of solubility, thus yin, yang ionic bond and fouling in the prevention system;
2) with the polymkeric substance of negatively charged ion or non-ionic type the suspended particle that can form dirt is surrounded, make it with enough identical charges, mutually exclusive and lose viscosifying power, make dirt particle stabilized in dispersion state;
3) can play destruction crystal ordered arrangement and lattice is distorted, distored effect takes place, crystal grain no longer increases in solid surface one-tenth dirt, 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 circulation number of times, after calcium ion concn improves, the possibility that forms fouling is arranged still.
5. ion exchange method: ion exchange method usually with sewage through necessary pre-treatment (filtering) as flocculation sediment after, pump into ion-exchange unit, through ion-exchange, remove the recirculated water that positively charged ion in the tap water obtains not having calcium.But this method cost is higher, and under higher calcium concn, the resin frequent regeneration can produce the new waste water of some amount, contaminate environment.
Lianyuan Iron and Steel Group Co., Ltd discloses a kind of pressure filter 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 step-down gear 4, agitator arm 7, paddle 5, sewage induction pipe 9, liquid medicine inlet pipe 2 etc. are formed.From the converter sewage of sewage induction pipe 9 with enter container 8 after the liquid medicine that contains polymeric flocculant from liquid medicine inlet pipe 2 mixes, under the effect of agitator arm 7 and paddle 5, make converter sewage and polymeric flocculant further mix the flocculation rate of accelerate sludge, enter into pressure filter 10 through effluent outfall 6, pressure filter 10 press filtrations are with mud in the sewage and water sepn, 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 that sewage that the flue gas during smelting spray pickling is produced is through neutralization, oxidation, sedimentary improvement.The steam cooling that the blast furnace drum is discharged changes water into, adds to cause casting slag machine in the supernatant treating 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, the supernatant treating water stores; The steam that the blast furnace drum is discharged is water through the interchanger cooling transformation, adds in the supernatant treating water, causes casting slag machine as water coolant, introduces the external crucible cinder notch and is used for the Water Quenching Slag water coolant.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 release, the present invention is the pollution treatment novel process 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 technology 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 smelting 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 processing, 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 technique 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 suspended solid 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 suspended substance 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 suspended substance, organism and bacterium, and get ultrafiltration dialysis liquid and concentrated solution.
5) nanofiltration (or reverse osmosis) is filtered: the dialyzate behind ultra-filtration filters is pumped into nanofiltration (or reverse osmosis) system filtration with topping-up pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration (or reverse osmosis) dialyzate and concentrated solution.
6) processing of concentrated solution: ultrafiltration and the merging of nanofiltration (or reverse osmosis) gained concentrated solution are stored in the tank, through the discharging of lime coagulation post precipitation.
In step 1), described water treatment coagulant is selected from polymerize aluminum chloride, 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 through the filtering sewage of fabric filter element directly by ultrafiltration membrane system filter dialyzate and concentrated solution.It is that molecular weight cut-off is 50000~300000 polysulphones hyperfiltration membrane, poly (ether-sulfone) ultrafiltration membrane, poly-fultolanil ultra-filtration membrane that described ultrafiltration system filters the ultra-filtration membrane that is adopted, cellulose acetate ultra-filtration membrane, polyvinylidene fluoride (PVDF) ultrafiltration membrane etc., its working conditions is a normal temperature, entrance pressure: 5~8bar, go out to press: 3.5~6.5bar, pressure difference is 1~1.5bar.
In step 5), it is that molecular weight cut-off is 150~300 polysulfones, polyethersulfone, cellulose acetate or composite nanometer filtering film etc. that described nanofiltration system is filtered selected mould material, its working conditions is: temperature: normal temperature, entrance pressure: 7~45bar, go out to press: 6~42.5bar, pressure difference pressure difference 1~1.5bar; Or reverse osmosis system to filter selected mould material be polysulfones, polyethersulfone, polymeric amide, cellulose acetate or composite nanometer filtering film etc., its working conditions is: temperature: normal temperature, entrance pressure: 7~20bar goes out to press: 6~19bar, pressure difference 1~1.5bar.Add the Scale inhibitors of 2~5mg/L in the dialyzate behind ultra-filtration filters.
Nanofiltration (or reverse osmosis) gained dialyzate (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 suspended substance, bacterium, macromolecular cpd, 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.
Embodiment
Embodiment 1: the sewage situation of certain smelting lead refinery is referring to table 1.
Table 1
Former water (mg/L) Behind original sewage treatment process (mg/L) Film is handled back (mg/L)
Total total plumbous SS Ca of the total zinc total mercury of the total arsenic of cadmium 2+ SO 4 2- CO 3 2- Cl - pH 0.5 1.0 20 0.05 35 50 500 600 30 900 7-8 0.01 0.4 1.8 0.03 0.05 20 500 1000 10 400 7-8 - - <1 - - - <50 <50 <10 <100 6-7
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 treating processes is as follows:
1) coagulation: the sewage with energy qualified discharge after the metallurgical works processing, by adding polymerize aluminum chloride 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 suspended solid 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 suspended substance 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.Mould material is a polyethersulfone, and molecular weight cut-off is 10000.Entrance pressure 5bar goes out to press 3.5bar.Remove materials such as small suspended substance, organism and bacterium and get ultrafiltration dialysis liquid and concentrated solution.By the dialyzate of control acquisition and the throughput ratio of concentrated solution, the rate of recovery 95% of control ultra-filtration filters.
5) nanofiltration is filtered: the dialyzate behind ultra-filtration filters is pumped into the nanofiltration system filtration with topping-up pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration dialyzate and concentrated solution.Mould material is a polysulfones, molecular weight cut-off 100.Entrance pressure 10bar goes out to press 8.5bar.By the dialyzate of control acquisition and the throughput ratio of concentrated solution, the filtering rate of recovery 70% of control nanofiltration.In the nanofiltration system operational process, add the Scale inhibitors of 2mg/L simultaneously.
The processing of concentrated solution: ultrafiltration and the merging of nanofiltration gained concentrated solution 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 dialyzate: nanofiltration gained dialyzate 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
Former water (mg/L) Behind original sewage treatment process (mg/L) Film is handled back (mg/L)
Total total plumbous SS Ca of the total zinc of the total magnesium of the total copper of cadmium 2+ SO 4 2- CO 3 2- Cl - pH 1.5 15 20 10 45 50 500 600 30 700 7-8 0.01 0.1 3.2 2 0.05 20 1500 700 10 600 7-8 - - - - - - <10 3 12 10 6-7
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 suspended solid 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 suspended substance 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.Mould material is a tetrafluoroethylene, and molecular weight cut-off is 20000.Entrance pressure 5bar goes out to press 3.5bar.Remove materials such as small suspended substance, organism and bacterium, get ultrafiltration dialysis liquid and concentrated solution.By the dialyzate of control acquisition and the throughput ratio of concentrated solution, the rate of recovery 95% of control ultra-filtration filters.
5) osmosis filtration: the dialyzate behind ultra-filtration filters is pumped into the reverse osmosis system filtration with topping-up pump, remove heavy metal, calcium ion plasma in the water, get reverse osmosis dialyzate and concentrated solution.Mould material is a cellulose acetate.Entrance pressure 7bar goes out to press 6bar.By the dialyzate of control acquisition and the throughput ratio of concentrated solution, the rate of recovery 65% of control osmosis filtration.In the reverse osmosis system operational process, add the Scale inhibitors of 3mg/L simultaneously in right amount.
The processing of concentrated solution: ultrafiltration and the merging of nanofiltration gained concentrated solution 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 dialyzate: nanofiltration gained dialyzate 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
The water quality standard of recirculated cooling water
Project Unit Require working conditions Permissible value
Suspended substance mg/L Determine according to manufacturing technique requirent ≤20
Heat-exchange equipment is board-like, fin-tube formula, spiral plate type ≤10
The pH value mg/L Determine according to medicine composition 7.0~ 9.2
Ca 2+ mg/L Determine according to reagent combination and working condition 30~200
Fe 2+ mg/L <0.5
CL - mg/L The carbon steel heat-exchange equipment ≤1000
The stainless steel heat-exchange equipment ≤300

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 suspended solid 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 suspended substance 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 suspended substance, organism and bacterium, and get ultrafiltration dialysis liquid and concentrated solution;
5) nanofiltration or osmosis filtration: the dialyzate behind ultra-filtration filters is pumped into nanofiltration or reverse osmosis system filtration with topping-up pump, remove heavy metal, calcium ion plasma in the water, get nanofiltration or reverse osmosis dialyzate and concentrated solution;
6) processing of concentrated solution: the processing of concentrated solution: ultrafiltration and nanofiltration or reverse osmosis gained concentrated solution 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), and described water treatment coagulant is selected from polymerize aluminum chloride, polyacrylamide or similar water treatment coagulant.
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 5-6bar condition, make through the filtering sewage of fabric filter element directly by ultrafiltration membrane system filter dialyzate and concentrated solution; It is that molecular weight cut-off is 50000~300000 polysulphones hyperfiltration membrane, poly (ether-sulfone) ultrafiltration membrane, poly-fultolanil ultra-filtration membrane that described ultrafiltration system filters the ultra-filtration membrane that is adopted, cellulose acetate ultra-filtration membrane or polyvinylidene fluoride (PVDF) ultrafiltration membrane.
4. as claim 1 or 3 described a kind of metal smelting factory sewage reclaiming methods based on membrane filtration technique, it is characterized in that in step 4), it is normal temperature that described ultrafiltration system filters the working conditions that is adopted, entrance pressure: 5~8bar, go out to press: 3.5~6.5bar, pressure difference is 1bar~1.5bar.
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 weight cut-off is 150~300 polysulfones, polyethersulfone, cellulose acetate or composite nanometer filtering film that described nanofiltration system is filtered selected mould 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 working conditions: temperature: normal temperature, entrance pressure: 7~45bar, go out to press: 6~42.5bar, pressure difference pressure difference 1bar~1.5bar.
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, polyethersulfone, polymeric amide, cellulose acetate or composite nanometer filtering film that described reverse osmosis system filters selected mould 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 filtering working conditions of described reverse osmosis system is: temperature: normal temperature, entrance pressure: 7~20bar, go out to press: 6~19bar, pressure difference 1~1.5bar.
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 Scale inhibitors of 2~5mg/L in the dialyzate 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.
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CN101857315A (en) * 2010-06-22 2010-10-13 赵胜利 Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration
CN101993160A (en) * 2010-10-21 2011-03-30 山东聊城倍杰特环保工程设计有限公司 Device and process for removing impurities from aluminum-containing waste water and recycling alkali
CN101659487B (en) * 2009-01-23 2011-07-27 云南祥云飞龙有色金属股份有限公司 Zero emission method of wastewater in lead-zinc metallurgical refinery
CN101200334B (en) * 2007-12-17 2011-09-21 金堆城钼业股份有限公司 Treatment method for molybdenum-containing acid wastewater
CN102219327A (en) * 2011-05-10 2011-10-19 中南大学 Membrane method treatment process for caprolactam waste water
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CN101659487B (en) * 2009-01-23 2011-07-27 云南祥云飞龙有色金属股份有限公司 Zero emission method of wastewater in lead-zinc metallurgical refinery
CN101857315A (en) * 2010-06-22 2010-10-13 赵胜利 Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration
CN101993160B (en) * 2010-10-21 2012-07-04 山东聊城倍杰特环保工程设计有限公司 Device and process for removing impurities from aluminum-containing waste water and recycling alkali
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CN102219327A (en) * 2011-05-10 2011-10-19 中南大学 Membrane method treatment process for caprolactam waste water
CN102219327B (en) * 2011-05-10 2013-01-09 中南大学 Membrane method treatment process for caprolactam waste water
CN102493793A (en) * 2011-12-30 2012-06-13 中国海洋大学 Method for preparing polymer solution for displacement of reservoir oil in oil field by membrane softening technology
CN102897944A (en) * 2012-07-30 2013-01-30 北京伊普国际水务有限公司 System for deeply processing difficultly degradable organic waste water
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CN109133421A (en) * 2018-09-21 2019-01-04 内蒙古兴安银铅冶炼有限公司 A kind of advanced treatment of wastewater recycling system

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