CN107512820B - Method for removing antimony in printing and dyeing wastewater - Google Patents
Method for removing antimony in printing and dyeing wastewater Download PDFInfo
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- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract
The invention discloses a method for removing antimony in printing and dyeing wastewater, which comprises the steps of adding excessive acid into alkali decrement wastewater and desizing wastewater, and carrying out acid precipitation treatment; treating dyeing wastewater by an adjusting tank, mixing the dyeing wastewater with wastewater after acid precipitation treatment, adding ferric polysulfate, adjusting the pH value, introducing into an air floatation tank, and recovering scum; adding liquid alkali into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank; after biochemical treatment, the wastewater enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter a biochemical tank, and separated wastewater is added with ferric polysulfate, the pH value is adjusted, and the wastewater is introduced into a tertiary sedimentation tank; the wastewater treated by the three sedimentation tanks meets the discharge requirement, and is directly discharged to the external environment or enters a workshop for recycling, and the sludge is incinerated. The method separates the high-concentration antimony-containing wastewater, treats the antimony by different qualities, uses polyferric sulfate as a flocculating agent, has good antimony adsorption effect, deeply removes antimony by a three-precipitation tank, has the antimony removal rate of up to 90 percent, and simultaneously has the COD removal rate in the wastewater of up to more than 90 percent.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a method for removing antimony serving as a metal element in textile printing and dyeing wastewater.
Background
Antimony is an amphoteric rare metal, and exists in various compound forms or in a suspended state or a dissolved state in an aqueous environment, and researches show that the antimony has chronic toxicity and carcinogenicity to organisms and human bodies. Antimony pollution in the environment comes from artificial pollution and natural pollution, and the pollution is mainly antimony-containing household garbage, dust, waste water, waste residues and the like in industrial operation; the natural pollution mainly refers to the phenomenon that the antimony content of the surrounding environment is higher due to special geological conditions of certain hot springs and geothermal zones in antimony-enriched areas such as antimony mine areas.
The united states environmental protection agency and the european union have listed antimony as a priority contaminant in 1979 and 1976, respectively, and the japanese sanitation office has also listed it as a contaminant of close concern. Strict environmental standards are established for antimony in all countries around the world. Germany stipulates that the average daily antimony absorption of a human body is 23 mu gSb/d. The European Union stipulates that the maximum allowable concentration of antimony in drinking water is 5. mu.g/L. 2. mu.g/L is defined in Japan. The U.S. environmental protection agency sets the MCLG (maximum conditioner level) and MCL (maximum conditioner level) values of antimony in drinking water to 6 mug/L. The antimony limit value is 5 mu g/L in the 'surface water environment quality standard' (GB3838-2002) and the 'sanitary standard for drinking water' (Ministry of health, 2001) in China. The 'urban water supply engineering planning code' (GB50282-98) stipulates that the antimony in the water outlet of a water plant is less than 10 mu g/L, and also stipulates that the antimony in a drinking water source is less than 50 mu g/L.
At present, antimony trioxide, antimony acetate or ethylene glycol antimony are added as catalysts for esterification polymerization reaction when 90% of polyester fibers are produced all over the world. In the dyeing process, residual antimony in the polyester fiber is transferred into printing and dyeing wastewater through alkali decrement process, desizing, high-temperature coloring and other processes. The environmental protection department of 4 months in 2015 modifies the discharge standard of pollutants for textile dyeing and finishing industry (GB4287-2012), and the discharge concentration of antimony in the direct discharge wastewater and the takeover of the printing and dyeing industry is 100 mug/L. The main source of antimony in the printing and dyeing wastewater is released in the processes of alkali decrement, whitening, desizing and dyeing of polyester fibers, wherein the total content in the decrement and desizing wastewater is at most 1000 mu g/L, and the content in the dyeing wastewater is about 200 mu g/L and 300 mu g/L. The problem that how to remove antimony deposited in printing and dyeing wastewater becomes a problem to be solved urgently for printing and dyeing enterprises is solved if the wastewater which does not reach the standard is discharged to seriously pollute surface water and underground water, and a method with a relatively ideal antimony removing effect is not available in the textile industry at present.
Disclosure of Invention
The invention aims to solve the problems that: provides a method for removing antimony in printing and dyeing wastewater.
In order to solve the problems, the technical scheme provided by the invention is that the method for removing antimony in the printing and dyeing wastewater comprises the following steps:
(1) adding excessive acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value, and performing acid precipitation treatment;
(2) mixing the wastewater after the acidification treatment with dyeing wastewater in a regulating tank, adding polyferric sulfate into the mixed wastewater, regulating the pH value, introducing into an air flotation tank, and recovering scum;
(3) after the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater treated by the biochemical tank enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, and the separated wastewater is added with ferric polysulfate, the pH value is adjusted, and then the wastewater is introduced into a tertiary sedimentation tank;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and sludge is subjected to landfill or incineration treatment.
Further, the pH value is adjusted to be 1.5-4 in the step (1).
Further, in the step (2), the PH value is adjusted to 3-6.
Further, in the step (4), the pH value is adjusted to 5-7.
Further, preferably, the pH value is adjusted to 2-3 in the step (1).
Further, preferably, the pH value is adjusted to 4.5-5.0 in the step (2).
Further, preferably, the pH value in the step (4) is adjusted to 6.2-6.5.
Further, polyacrylamide is added into the mixed wastewater in the step (2).
Further, preferably, the adding amount of the ferric polysulfate in the step (2) is 1 per mill to 1.5 per mill of the mass of the mixed wastewater.
Further, polyacrylamide is added into the wastewater separated in the step (4).
Further, the adding amount of the ferric polysulfate in the step (4) is 1.5-3 per mill of the mass of the separated wastewater.
Further, preferably, the acid added in step (1) is sulfuric acid.
The invention has the advantages that:
1. the method separates the antimony-containing wastewater with high alkali decrement and desizing concentration from the antimony-containing wastewater with low dyeing concentration for quality separation treatment, and has strong pertinence and high antimony removal efficiency; the flocculating agent adopts ferric polysulfate, which has higher adsorption flocculation effect on antimony in the wastewater; the antimony removal rate after acid precipitation and air floatation treatment reaches 85%, the method further designs three sedimentation tank deep treatment, and antimony is removed by flocculation adsorption through secondary addition of ferric polysulfate, so that the antimony removal effect is good, and the removal rate is as high as 90%; meanwhile, the method also removes COD in the wastewater at one time, and the removal rate is up to more than 90%.
2. In the traditional sewage treatment, the scum after the acid precipitation treatment needs to be additionally provided with a precipitation or air floatation device for separating sludge, the sludge has extremely high corrosivity and viscosity, the filter press is corroded in the sludge dewatering link, and the filter cloth of the filter press is polluted and blocked, which is a troublesome problem in the traditional process. The method changes the traditional thinking, the sludge and the wastewater after the acidification treatment are mixed with the dyeing wastewater and then subjected to air floatation, and the separation is completed in one air floatation or sedimentation equipment, so that the process flow is shortened, the working intensity is reduced, the cost is low, and the effect is good.
3. The equipment applied by the method is conventional equipment of a dye printing factory or a sewage treatment plant, and can be realized by reasonably setting the process flow, so that the method is convenient to popularize and apply, and the equipment configuration cost of the factory is low.
Drawings
The invention will be further described with reference to the accompanying drawings and examples
FIG. 1 is a process flow diagram of the method for removing antimony from printing and dyeing wastewater.
Detailed Description
Example 1 in this example, the method for removing antimony from printing and dyeing wastewater comprises the following steps:
(1) adding excessive sulfuric acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value to be 2, and carrying out acid precipitation treatment; usually, the alkali decrement and desizing wastewater is strongly alkaline, COD accounts for about 50% of the printing and dyeing wastewater COD, and the content of antimony accounts for 70%. In the step, COD is removed by more than 90%, and antimony is removed by about 30%.
(2) Mixing the wastewater after the acid precipitation treatment with dyeing wastewater in a regulating reservoir, adding polyferric sulfate and polyacrylamide into the mixed wastewater, wherein the adding amount of the polyferric sulfate is 1.5 per mill of the mass of the wastewater, regulating the pH value to be 5.0, then introducing into an air flotation tank, and recovering scum; in the step, the removal rate of COD is about 45 percent, and the removal rate of antimony is about 85 percent.
(3) After the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater treated by the biochemical tank enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, biochemical treatment is repeatedly carried out, wherein, ferric polysulfate and polyacrylamide are added into the separated wastewater, the adding amount of the ferric polysulfate is 1.5 per mill of the quality of the separated wastewater, the PH value is adjusted to 6.2, and then the wastewater is introduced into a tertiary sedimentation tank for antimony removal advanced treatment;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and the sludge is subjected to landfill or incineration treatment.
The COD removal rate of the wastewater treated by the method is up to more than 90 percent, and the antimony removal rate can reach 90 percent. Usually, the COD concentration in the treated wastewater is stabilized below 50mg/L, the antimony content is as low as about 14 mu g/L and is far lower than the limit index of 100 mu g/L of metallic antimony in wastewater discharged according to the requirements of the discharge Standard of pollutants for textile dyeing and finishing industry (GB4287-2012), and the antimony content in the wastewater treated by the method provided by the invention is stable and reaches the standard and can be directly discharged to an external environment.
Example 2: in this embodiment, the method for removing antimony from the printing and dyeing wastewater includes the following steps:
(1) adding excessive sulfuric acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value to 3, and carrying out acid precipitation treatment; usually, alkali decrement and desizing wastewater is usually strong alkali, COD accounts for about 50% of printing and dyeing wastewater COD, and antimony content accounts for 70%. In the step, COD is removed by more than 90%, and antimony is removed by about 30%.
(2) Mixing the wastewater after the acid precipitation treatment with dyeing wastewater in an adjusting tank, adding polyferric sulfate and polyacrylamide into the mixed wastewater, wherein the adding amount of the polyferric sulfate is 1 per mill of the mass of the wastewater, adjusting the pH value to 4.5, then introducing into an air flotation tank, and recovering scum; in the step, the removal rate of COD is about 45 percent, and the removal rate of antimony is about 85 percent.
(3) After the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater treated by the biochemical tank enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, biochemical treatment is repeatedly carried out, wherein, ferric polysulfate and polyacrylamide are added into the separated wastewater, wherein the ferric polysulfate accounts for 3 per mill of the mass of the separated wastewater, the PH value is adjusted to 6.5, and then the wastewater is introduced into a tertiary sedimentation tank for antimony removal advanced treatment;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and the sludge is subjected to landfill or incineration treatment.
The COD removal rate of the wastewater treated by the method reaches over 90 percent, and the antimony removal rate reaches 90 percent. The COD concentration in the wastewater is below 50mg/L, and the content of antimony is as low as about 14 mu g/L.
Example 3: in this embodiment, the method for removing antimony from the printing and dyeing wastewater includes the following steps:
(1) adding excessive sulfuric acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value to 1.5, and carrying out acid precipitation treatment; usually, alkali decrement and desizing wastewater is usually strong alkali, COD accounts for about 50% of printing and dyeing wastewater COD, and antimony content accounts for 70%. In the step, COD is removed by more than 90%, and antimony is removed by about 30%.
(2) Mixing the wastewater after the acid precipitation treatment with dyeing wastewater in an adjusting tank, adding polyferric sulfate and polyacrylamide into the mixed wastewater, wherein the adding amount of the polyferric sulfate is 1.2 per mill of the mass of the wastewater, adjusting the pH value to 3, introducing into an air flotation tank, and recovering scum;
(3) after the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater treated by the biochemical tank enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, biochemical treatment is repeatedly carried out, wherein, ferric polysulfate and polyacrylamide are added into the separated wastewater, the adding amount of the ferric polysulfate is 2.0 per mill of the mass of the separated wastewater, the PH value is adjusted to 7, and then the wastewater is introduced into a tertiary sedimentation tank for antimony removal advanced treatment;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and the sludge is subjected to landfill or incineration treatment.
The COD removal rate of the wastewater treated by the method is up to 90%, the antimony content is far lower than the limit index of 100 mu g/L of metallic antimony in the wastewater required to be discharged by the discharge standard of pollutants for textile dyeing and finishing industry (GB4287-2012), and the antimony content of the wastewater treated by the method is stable and reaches the standard and can be directly discharged to the external environment.
Example 4: in this embodiment, the method for removing antimony from the printing and dyeing wastewater includes the following steps:
(1) adding excessive sulfuric acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value to be 4, and carrying out acid precipitation treatment; usually, alkali decrement and desizing wastewater is usually strong alkali, COD accounts for about 50% of printing and dyeing wastewater COD, and antimony content accounts for 70%. In the step, COD is removed by more than 90%, and antimony is removed by about 30%.
(2) Mixing the wastewater after the acid precipitation treatment with dyeing wastewater in an adjusting tank, adding polyferric sulfate and polyacrylamide into the mixed wastewater, wherein the adding amount of the polyferric sulfate is 1.5 per mill of the mass of the wastewater, adjusting the pH value to be 6, then introducing into an air flotation tank, and recovering scum;
(3) after the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater treated by the biochemical tank enters a secondary sedimentation tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, biochemical treatment is repeatedly carried out, wherein, ferric polysulfate and polyacrylamide are added into the separated wastewater, the adding amount of the ferric polysulfate is 3 per mill of the mass of the separated wastewater, the PH value is adjusted to 5, and then the wastewater is introduced into a tertiary sedimentation tank for antimony removal advanced treatment;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and the sludge is subjected to landfill or incineration treatment.
The COD removal rate of the wastewater treated by the method is up to 90%, the antimony content is far lower than the limit index of 100 mu g/L of metallic antimony in the wastewater required to be discharged by the discharge standard of pollutants for textile dyeing and finishing industry (GB4287-2012), and the antimony content of the wastewater treated by the method is stable and reaches the standard and can be directly discharged to the external environment.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for removing antimony in printing and dyeing wastewater is characterized by comprising the following steps:
(1) adding excessive acid into the alkali decrement wastewater and the desizing wastewater, adjusting the pH value, and performing acid precipitation treatment;
(2) mixing the wastewater after the acidification treatment with dyeing wastewater in an adjusting tank, adding polyferric sulfate into the mixed wastewater, adjusting the pH value, introducing into an air flotation tank, and recovering scum;
(3) after the treatment in the air flotation tank is finished, adding liquid caustic soda into the wastewater, introducing the wastewater into a hydrolysis tank for hydrolysis acidification treatment, collecting waste gas, and continuously introducing the wastewater into a biochemical tank;
(4) the wastewater enters a secondary sedimentation tank after being treated by a biochemical tank, sludge separated in the secondary sedimentation tank flows back to enter the biochemical tank, and the separated wastewater is added with ferric polysulfate, is adjusted in pH value and then enters a tertiary sedimentation tank;
(5) the wastewater treated by the three sedimentation tanks meets the discharge requirement, is directly discharged to an external environment or enters a workshop for recycling, and sludge is subjected to landfill or incineration treatment.
2. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that in the step (1), the pH value is adjusted to 1.5-4; adjusting the pH value to 3-6 in the step (2); and (4) adjusting the pH value to 5-7.
3. The method for removing antimony from printing and dyeing wastewater according to claim 1 or 2, characterized in that in the step (1), the pH value is adjusted to 2-3; adjusting the pH value to 4.5-5.0 in the step (2); and (4) adjusting the pH value to 6.2-6.5.
4. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that polyacrylamide is further added to the mixed wastewater in the step (2).
5. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that the ferric polysulfate added in step (2) is 1 to 1.5 per mill of the mass of the mixed wastewater.
6. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that polyacrylamide is further added to the wastewater separated in step (4).
7. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that the ferric polysulfate added in step (4) is 1.5-3% of the mass of the separated wastewater.
8. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that the acid added in step (1) is sulfuric acid.
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| CN108946873A (en) * | 2018-06-19 | 2018-12-07 | 苏州新能环境技术股份有限公司 | A kind of technique that embrane method processing alkali decrement waste water realizes lye reuse and antimony removal |
| CN108751611B (en) * | 2018-07-13 | 2024-04-12 | 苏州新工环境工程技术有限公司 | Efficient printing and dyeing wastewater treatment system and treatment method thereof |
| CN109052731B (en) * | 2018-09-14 | 2021-11-26 | 杭州开源环保工程有限公司 | Method for efficiently removing antimony from printing and dyeing wastewater |
| CN109970278B (en) * | 2019-04-10 | 2020-11-03 | 浙江大学 | Method and equipment for efficiently and economically removing antimony in printing and dyeing wastewater |
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