CN1931729A - Process of treating and utilizing acid waste water containing heavy metal - Google Patents
Process of treating and utilizing acid waste water containing heavy metal Download PDFInfo
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- CN1931729A CN1931729A CN 200610041752 CN200610041752A CN1931729A CN 1931729 A CN1931729 A CN 1931729A CN 200610041752 CN200610041752 CN 200610041752 CN 200610041752 A CN200610041752 A CN 200610041752A CN 1931729 A CN1931729 A CN 1931729A
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Abstract
The process of treating and utilizing acidic waste water containing heavy metal includes the following steps: filtering the acidic waste water containing heavy metal in two filters with specific material; 2. purifying water and producing acid; and 3. reutilizing the treated waste water with relatively low acid concentration. The present invention has low cost, saving in resource, long equipment service life, high treating effect and other advantages.
Description
Technical Field
The invention relates to a method for treating and utilizing acid wastewater containing heavy metals generated in the processes of smelting, chemical engineering, metal processing, mining and other industrial production.
Background
In the production process of the industries such as smelting, chemical engineering, metal processing, mines and the like in China, a large amount of water resources can be consumed, and a large amount of acid wastewater containing heavy metal ions can be generated. Because of the insufficient technology and investment, the recycling cost is high, heavy metals in the wastewater are difficult to recycle, and the wastewater cannot be recycled well. For the treatment of such wastewater, there are various methods in China at present. Such as: neutralization precipitation, sulfidation precipitation, redox, iron oxidation, flotation, adsorption, bioflocculation, ion exchange, etc. However, the neutralization method is still commonly used, and the process flow is as follows: heavy metal acid wastewater → a grit chamber → a mixing reaction chamber (adding lime milk → a sedimentation tank → purified water → discharge. The lime neutralization method for treating the acid wastewater containing heavy metal ions is an old method. It has been widely used so far because it has a high removal rate (more than 99%) for heavy metal ions and can treat almost all heavy metal ions except mercury. However, the method has the disadvantages of poor labor sanitary conditions, resource waste, high treatment cost, large volume of generated sludge, difficult treatment, strong corrosivity and the like. For example:
a. after the waste water is neutralized by lime, the heavy metal hydroxide-alum floc is produced, which has small specific gravity and is easy to be broken into small particles during strong stirring or conveying, so its settling speed is slow. Often overflow along with water flow in the process of sedimentation separation, and the turbidity of the treated wastewater is increased, and the heavy metal ions still exceed the standard. The settled alum blossom or neutralized slag mud has extremely high water content (more than 99 percent), poor filtering and dehydrating performance, complex composition and low heavy metal content grade, which brings difficulty to comprehensive recycling and disposal and even causes secondary pollution;
b. the acid wastewater containing heavy metals can be treated by a lime method to obtain purified water, so that the discharge of industrial wastewater is reduced. However, the purified water has high pH value and calcium ion content, which easily causes serious scaling of purified water delivery pipelines and water using equipment, and restricts the recycling of the purified water. The scale is solved, a water quality stabilizer needs to be added into the reclaimed water, although the problem of obvious scale can be solved, the treatment cost is increased, and the phosphorus-containing water quality stabilizer can cause the phosphorus content in the discharged water to exceed the standard;
c. when the concentration of heavy metal ions contained in the acidic wastewater is high and the components are complex, the removal of various heavy metal ions in the water cannot be realized at one time only depending on a certain pH value condition, the pH value needs to be set in each stage of neutralization tank, the treatment cost is increased, errors exist in the detection process, the detection signal lags, and the removal effect of the heavy metal ions can be influenced;
d. the calcium neutralizing materials such as lime milk and the like have strong corrosivity and have certain dangerousness in the transportation, use and storage processes. Corrosion and blockage of equipment can be caused in the using process, and the treatment cost is increased in maintenance;
e. due to the adoption of a chemical method for treatment, the components in the sludge are complex, and heavy metal elements have complex valence states and forms, are mostly indissolvable substances and are difficult to recover, so that the resource waste is caused.
According to data, only one discharge amount of acid waste water is considerable when the acid waste water is smelted in China every year, the annual water consumption of 12 domestic large heavy metal nonferrous enterprises is about 11786.41 hundred million tons, the industrial reuse water consumption is about 9194.81 million tons, and the reuse rate is only 78%. The annual discharged industrial wastewater amount reaches 1797.51 hundred million tons, the standard discharge rate of the wastewater is only 73 percent, not only causes resource waste, but also pollutes nearby water bodies, and is an important factor influencing the improvement of the reuse rate of industrial water. And a large amount of pickling wastewater is generated in the industries of chemical engineering, metal processing, mines and the like. Due to the above problems in the treatment process, a great waste of resources and serious pollution to the environment are caused. Therefore, the purification treatment of the heavy metal-containing acidic wastewater is a problem which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the problems of the existing metal acidic wastewater treatment, the invention develops a new method, adopts a physical method and provides a method for treating and utilizing the heavy metal-containing acidic wastewater. Fundamentally solves the problems of resource waste and possible environmental pollution in the treatment process of the acid wastewater containing the heavy metals, and achieves the aim of recycling the metal acid wastewater resources.
The invention adopts a novel filtering technology to design a process method, can effectively treat the acidic wastewater containing heavy metals generated in the production processes of industries such as smelting, chemical engineering, metal processing, mines and the like, and can recover and treat substances such as heavy metals in filter residues and further take measures to recycle; meanwhile, the recycling of purified water is realized, and the water consumption in the whole production process is reduced; the effect of recycling the acid in the acidic wastewater is achieved. The method has the advantages of low operation cost, material saving, simple operation and maintenance, better water and energy saving effects and better economic and environmental benefits.
The object of the invention can be achieved by the following measures:
a method for treating and utilizing acid wastewater containing heavy metals comprises the following steps:
(1) the acid wastewater containing heavy metal is sent into a ceramic filter material filtering facility
Acid wastewater containing heavy metals generated in the production process of preparing acid from smelting flue gas is precipitated by a precipitation tank 1 and then enters a ceramic filter material filtering facility 5 for filtering. The wastewater flows in from a water inlet a at the upper part of the filtering facility and flows downwards in sequence through a ceramic filter material layer c and a supporting layer d, impurities such as suspended substances in the wastewater are intercepted by the mechanical screening, precipitation, diffusion, transfer, electrostatic adsorption and the like of the filter material layer, and the filtered clean water enters a lower empty bin e and is supplied out through a water outlet b.
In order to ensure the normal work of the filtering facility, an acting water head between 0.1 and 0.8m is kept above the filtering layer. The grain size of the filter material can be 0.2-5.0mm, the thickness of the filter layer is 0.35-1.50m, the support layer is a ceramic filter plate, and the flow rate of the filtration is 2-20 m/h.
And during the back flushing of the filtering facility, closing the water inlet valve, and after the treated water in the filtering pond is emptied, the flushing water and the air enter the upward flushing filtering layer from the step b.
(2) The filtrate with higher acid concentration passing through the outlet of the ceramic filter material filtering facility is purified by ultrafiltration membrane equipment
When the acid concentration of the filtrate generated after being filtered by the ceramic filter material filtering facility reaches 5-15%, the filtrate is processed by an ultrafiltration membrane device 3. The ultrafiltration technology adopts a hollow fiber tube membrane made of acetate fiber. The water entering the hollow fiber tube membrane is driven by pressure from the inner surface of the hollow fiber tube to permeate the ultrafiltration membrane under the pressure condition of 0.1-4.0Mpa, and flows out from the outer surface; the filtered clean water is collected in the filter cylinder and is discharged from the water discharge port; suspended substances and polymer solutes larger than the membrane pores are retained by the membrane and discharged as a concentrated solution from the other end.
The sludge containing heavy metals intercepted when passing through the ceramic filter material filtering facility and the ultrafiltration membrane equipment can be dehydrated and collected by a filter-pressing dehydrator 2 and then recycled to remove water and heavy metal substances.
(3) Purifying water to prepare acid
When the acid concentration of the purified water treated by the ultrafiltration membrane equipment is higher than 5 percent, introducing the purified water into an absorption tower 4 of 98 percent concentrated sulfuric acid solution to generate reaction Absorbing and preparing acid.
(4) Treatment of the filtrate having a lower acid concentration at the outlet of the ceramic filter material filtration plant
When the acid concentration in the filtrate treated by the ceramic filter material filtering facility is lower than 5 percent, the part of the acid wastewater is returned to the water inlet after being utilized by the sulfuric acid purification process 6, the acid wastewater with higher acid concentration is generated, and the operations of the steps (1) to (3) are repeated.
The advantages and the beneficial effects of the invention are as follows:
(1) the method can effectively treat the acidic wastewater containing heavy metals generated in the production processes of industries such as smelting, chemical engineering, metal processing, mines and the like (see table 1).
Table 1: ceramic filter material and ultrafiltration membrane for removing heavy metal acidic wastewater
As can be seen from table 1, the removal rate of the ceramic filter material filtering facility on the suspended solids is 88%, and the removal rate of the suspended solids reaches more than 99.3% through ultrafiltration membrane filtering; the recovered sludge can be further recycled by taking measures; meanwhile, the reuse rate of the purified water is up to more than 90%, and the water consumption in the whole production process is reduced; the effect of recycling the acid in the acidic wastewater is achieved.
(2) The ceramic filter material and the ultrafiltration membrane material adopted in the method are commonly selected materials in the wastewater treatment process in recent years. The ceramic filter material filtering facility has good water-saving and energy-saving effects, and can prolong the service life of the filtering equipment; the sewage treatment device has strong sewage interception capability and adsorption capability, has a good removal effect on suspended matters in water, and is stable in treatment effect and good in backwashing effect. The filtered waste water meets the requirement of purified water.
Preparing ultrafiltration membranes with different pore diameters according to actual needs. The ultrafiltration membrane technology uses pressure as a driving force in the wastewater treatment process, after the wastewater is filtered, solid suspended matters and macromolecular solutes are intercepted, and water permeates through the membrane to realize the purification of the wastewater. The effluent meets the requirement of water for directly preparing acid.
(3) The ceramic filter material filtering facility and the ultrafiltration membrane device in the equipment are all provided with cleaning equipment. Through the processes, the purification and the recycling of the acid wastewater containing the heavy metals are finally realized, the influence on the environment is reduced, and meanwhile, corresponding economic benefits are generated.
In conclusion, the method for treating the acid wastewater containing the heavy metals can achieve the aims of reducing the treatment cost, saving resources, recycling and comprehensively utilizing the wastewater and protectingthe environment, and realizes the unification of economic benefits and environmental benefits.
Drawings
FIG. 1 is a schematic view of a ceramic filter material filtering facility according to the present invention
In the figure: a. water inlet
b. Water outlet (flushing water inlet)
c. Ceramic filter material layer
d bearing layer
e. Lower empty bin
FIG. 2 is a process flow diagram of the present invention
In the figure: 1. sedimentation tank
2. Sludge collection
3. Ultrafiltration membrane device
4. Concentrated sulfuric acid (98%) absorption tower
5. Ceramic filter material filtering facility
6. Sulfuric acid purification procedure
Detailed Description
The invention will be further described with reference to the following drawings:
as shown in the figures 1 and 2, the purified washing wastewater is generated in the production process of preparing acid by smelting flue gas, and the water amount is 80-100 m3And h, acid content is about 0.7 percent, total suspended matter (ss) is 2480mg/L, and acid wastewater containing heavy metals such as Cu, Ni, Pb, Ca and the like is precipitated by a sedimentation tank 1 and then enters a ceramic filter material filtering facility 5 for filtering. The waste water flows in from a water inlet a at the upper part of the filtering facility and flows downwards through a ceramic filtering material layer c and a ceramic filtering plate d, wherein the filtering material particle size of the ceramic filtering material layer c is 2.0mm, and the thickness of the filtering layer is 0.70 m. At the filtering speed of 6m/h, impurities such as suspended substances, macromolecular particles with the particle size of 0.2-1.0mm and the like in water are intercepted by the mechanical screening (the particles are larger than the aperture or are directly intercepted by gaps among deposited particles), sedimentation, diffusion, transfer, electrostatic adsorption and the like of a filter material layer, and filtered clean water enters a lower empty bin e and is supplied out through a water outlet b.
In order to ensure the normal work of the filtering facility, an acting water head between 0.1 and 0.8m is kept above the filtering layer. During the back flushing of the filtering facility, the water inlet valve is closed first, and after the treated water in the filtering pond is emptied, the flushing water and air enter the upward flushing filtering layer from the step b.
When the acid concentration of the filtrate generated after being filtered by the ceramic filter material filtering device 5 exceeds 5 percent, the filtrate is processed by the ultrafiltration membrane device 3.
When in use, the water inflow is 5m under the pressure of 0.6MPa3The filtrate generated after being filtered by the ceramic filter material filtering device 5 passes through an ultrafiltration membrane with the aperture of 0.1 mu m from the inner surface of the hollow fiber tube through pressure drive and flows out from the outer surface; collecting the filtered purified water in the filter cylinder, and outputting the acid from a water outlet; the suspended solid and the macromolecular solute larger than the membrane aperture are intercepted bythe membrane and are discharged from the other end as concentrated solution.
Ultrafiltration membrane materialAdopts cellulose acetate derivative (CA) as acid-resistant and corrosion-resistant material, and has a membrane flux of 1.0m3/(m2·h)。
The sludge containing heavy metals intercepted when passing through the ceramic filter material filtering facility 5 and the ultrafiltration membrane equipment 3 can be dewatered and collected by a filter-pressing dehydrator, and the collected sludge is sent to a smelting system for recycling.
The removal rate of the solid suspended matters and the macromolecular particles by the ceramic filter material filtering facility 5 can reach more than 88 percent, and the residual rate of the solid suspended matters and the macromolecular solutes in the purified water after the purification by the ultrafiltration membrane device 4 is lower than 1 percent.
The acid concentration in the purified water outlet filtrate treated by the ceramic filter material filtering facility 5 and the ultrafiltration membrane equipment 3 is higher than 5 percent and is sent into the absorption tower 4 when meeting the requirement of acid making water, and the filtrate with the acid concentration higher than 5 percent and the concentrated sulfuric acid solution with the acid concentration of 98 percent are respectively sprayed down from the top of the absorption tower 4 to generate reaction. The reaction formula is as follows: absorbing acid, and enabling a finished product to flow out from the bottom of the tower.
When the acid concentration of the filtrate passing through the outlet of the ceramic filter material filtering facility 5 is lower than 5 percent, the part of the acid wastewater is returned to thewater inlet after being utilized by the sulfuric acid purification process 6, and the operation of the steps is repeated for the generated acid wastewater with higher acid concentration.
The recovery rate of acid in the process reaches more than 90%, and the utilization rate of return water reaches more than 90%.
Claims (3)
1. A method for treating and utilizing acid wastewater containing heavy metals is characterized by comprising the following steps:
acid wastewater containing heavy metals is generated in the production process of producing acid by smelting flue gas, and is filtered by a ceramic filter material filtering facility (5) after being precipitated, and suspended substances and macromolecular particulate impurities in the water are intercepted by a filter material layer; when the acid concentration of the filtrate generated after being filtered by the ceramic filter material filtering facility (5) reaches 5-15%, the filtrate is treated by an ultrafiltration membrane device (3); the sludge containing heavy metals intercepted when passing through a ceramic filter material filtering facility (5) and an ultrafiltration membrane device (3) is dehydrated, collected and recycled (2); when the purified water treated by the ultrafiltration membrane equipment (3) meets the requirement of water for acid production, introducing an absorption tower (4) of 98% concentrated sulfuric acid solution to absorb acid production; when the acid concentration of the filtrate passing through the outlet of the ceramic filter material filtering facility (5) is lower than 5 percent, the filtrate is returned to the water inlet after being utilized by the sulfuric acid purification process (6).
2. A method according to claim 1, wherein the filtering material in the filtering means is quartz sand or garnet, but preferably ceramic filtering material, the grain size of which can be 0.2-5.0mm, and the thickness of the filtering layer is 0.35-1.50 m. The acting water head between 0.1 and 0.8m is kept above the filtering layer.
3. A process according to claim 1, wherein the support layer of the filtering means is a corrosion-resistant filter plate, preferably a ceramic filter plate, and the flow rate of the filtering is 2-20 m/h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100417528A CN100400427C (en) | 2006-01-24 | 2006-01-24 | Process of treating and utilizing acid waste water containing heavy metal |
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| CNB2006100417528A CN100400427C (en) | 2006-01-24 | 2006-01-24 | Process of treating and utilizing acid waste water containing heavy metal |
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| CN1931729A true CN1931729A (en) | 2007-03-21 |
| CN100400427C CN100400427C (en) | 2008-07-09 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101731A (en) * | 2011-01-14 | 2011-06-22 | 韶关市雅鲁环保实业有限公司 | Mine wastewater treatment device and treatment method thereof |
| CN103304090A (en) * | 2013-06-07 | 2013-09-18 | 刘世斌 | Device and method for recycling waste sulfate in sulfate acid-making system |
| CN108939705A (en) * | 2017-05-29 | 2018-12-07 | 黄华丽 | The purification method and device of smog in a kind of air-flow |
| CN110201448A (en) * | 2019-06-12 | 2019-09-06 | 安徽省宁国市立盛汽车电器有限责任公司 | A kind of electrophoresis part cleaning wastewater circulation device and decontamination cycle method |
| CN111592186A (en) * | 2020-05-22 | 2020-08-28 | 南昌航空大学 | Slag heavy metal pollution source control barrier and application thereof |
| CN114588694A (en) * | 2022-03-12 | 2022-06-07 | 许剑枫 | Cutting fluid recycling system for machine tool |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180994C (en) * | 2003-05-16 | 2004-12-22 | 天津大学 | Method for increasing waste water treating efficiency by improving activity of sulfate reducing bacteria |
| CN100336746C (en) * | 2005-05-12 | 2007-09-12 | 邯郸钢铁股份有限公司 | Method of preparing pure water using metallurgic sewage |
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2006
- 2006-01-24 CN CNB2006100417528A patent/CN100400427C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101731A (en) * | 2011-01-14 | 2011-06-22 | 韶关市雅鲁环保实业有限公司 | Mine wastewater treatment device and treatment method thereof |
| CN102101731B (en) * | 2011-01-14 | 2012-05-30 | 韶关市雅鲁环保实业有限公司 | Mine wastewater treatment device and treatment method thereof |
| CN103304090A (en) * | 2013-06-07 | 2013-09-18 | 刘世斌 | Device and method for recycling waste sulfate in sulfate acid-making system |
| CN103304090B (en) * | 2013-06-07 | 2014-11-05 | 刘世斌 | Device and method for recycling waste sulfate in sulfate acid-making system |
| CN108939705A (en) * | 2017-05-29 | 2018-12-07 | 黄华丽 | The purification method and device of smog in a kind of air-flow |
| CN110201448A (en) * | 2019-06-12 | 2019-09-06 | 安徽省宁国市立盛汽车电器有限责任公司 | A kind of electrophoresis part cleaning wastewater circulation device and decontamination cycle method |
| CN111592186A (en) * | 2020-05-22 | 2020-08-28 | 南昌航空大学 | Slag heavy metal pollution source control barrier and application thereof |
| CN114588694A (en) * | 2022-03-12 | 2022-06-07 | 许剑枫 | Cutting fluid recycling system for machine tool |
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| CN100400427C (en) | 2008-07-09 |
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