CN113045029A - Treatment method of paint spraying wastewater - Google Patents
Treatment method of paint spraying wastewater Download PDFInfo
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- CN113045029A CN113045029A CN202011481447.7A CN202011481447A CN113045029A CN 113045029 A CN113045029 A CN 113045029A CN 202011481447 A CN202011481447 A CN 202011481447A CN 113045029 A CN113045029 A CN 113045029A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to the technical field of wastewater recycling treatment, in particular to a method for treating paint spraying wastewater, which comprises the following steps: acid precipitation treatment, salting-out treatment, reduced pressure evaporation treatment and Fenton oxidation treatment. The invention aims to provide a method for treating paint spraying wastewater, which has the advantages of generating less waste residues, removing resin and most of organic solvents in the paint spraying wastewater, and directly performing biochemical treatment without dilution, wherein the final treated effluent has the characteristics of low organic matter concentration, good biodegradability and the like; meanwhile, the inorganic salt used in the treatment process can be recycled, so that the treatment cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of wastewater recycling treatment, in particular to a method for treating paint spraying wastewater.
Background
Paint spraying is one of the important processes in manufacturing industry, a large amount of paint mist and organic solvent exhaust gas are generated in the paint spraying process, the paint mist and the organic solvent exhaust gas are toxic and inflammable and explosive, and in order to reduce the danger of a paint spraying workshop and prevent the paint mist and the organic solvent exhaust gas from polluting the surrounding environment, the air in a working area of a paint spraying room is generally washed by water, so that the paint mist and the organic solvent exhaust gas in the air are transferred into water, thereby forming paint spraying waste water.
The paint spraying waste water contains a large amount of resin and solvent, and a small amount of pigment, filler and surfactant. The resin in the wastewater is usually epoxy resin, polyurethane resin, polyacrylic resin, polybutadiene resin, phenolic resin and the like; the solvent comprises butyl acetate, ethyl propionate, ethyl acetate, ethylene glycol butyl ether acetate, 1-ethoxypropanol acetate, ethylene glycol butyl ether, ethylene glycol ethyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, isopropanol, n-butanol, isobutanol and other organic matters.
The resin, pigment and filler in the paint spraying waste water are formed into a resin colloid coated with a layer of hydrated interface film with same charges under the action of surfactant, solvent and the like, and the colloid can not be adhered to each other due to repulsion of the same charges, so that the paint spraying waste water is in a sol state. The paint spraying wastewater has the characteristics of high COD, poor biodegradability, complex pollutant components and the like, and can cause severe water body pollution when being directly discharged.
Chinese patent publication No. CN106396181A discloses a method and a system for treating high-concentration organic wastewater, which comprises chemically oxidizing spray paint wastewater (COD 35000mg/L, salt content 20%), mixing with electrophoresis wastewater and other wastewater, adding coagulant for coagulating sedimentation, and performing biochemical treatment to obtain final effluent with COD of 8mg/L and salt content of 1%.
The Chinese patent document with the publication number of CN201310695939.X discloses a paint spraying wastewater treatment process, wherein the paint spraying wastewater is subjected to acidification, demulsification and coagulation pretreatment, COD is reduced to 13000mg/L from 22630mg/L, and then is subjected to further advanced treatment by hydrolytic acidification, anaerobic treatment, aerobic treatment and biological filter, and the COD is reduced to below 300mg/L, so that the paint spraying wastewater reaches the GB8978-1996 three-level discharge standard.
The Chinese patent document with publication number CN110040870A discloses a method for treating paint spraying wastewater, wherein the COD of the effluent is reduced to be below 100mg/L after the paint spraying wastewater is subjected to aeration, oxidation and coagulation treatment, and the effluent reaches the GB 110040870A-1996 three-level discharge standard.
Therefore, the existing paint spraying wastewater treatment system or technology has the following problems:
(1) a large amount of coagulant is used, so that a large amount of coagulation waste residues are generated, and secondary pollution to the environment is caused;
(2) the removal rate of the organic solvent is low, so that the problems of high dilution factor, large organic load and the like exist in the subsequent biochemical treatment process.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a method for treating paint spraying wastewater, which generates less waste residues, can remove resin and most of organic solvents in the paint spraying wastewater, has the characteristics of low organic matter concentration, good biodegradability and the like in the final treated effluent, and can carry out direct biochemical treatment without dilution; meanwhile, the inorganic salt used in the treatment process can be recycled, so that the treatment cost is greatly reduced, and the resourceful treatment of the paint spraying wastewater is realized.
The technical purpose of the invention is realized by the following technical scheme, and the method for treating the paint spraying wastewater comprises the following steps:
s1, acid precipitation treatment: adding inorganic acid into the paint spraying wastewater to adjust the pH, heating for reaction, and filtering to obtain a first solution;
s2, salting out treatment: adding inorganic base into the first solution, adjusting the pH value to be neutral, then adding inorganic salt, heating for dissolving, standing for layering, removing an upper organic phase separated out by the solvent, and collecting a lower aqueous phase as a second solution;
s3, reduced pressure evaporation treatment: carrying out reduced pressure evaporation on the second solution, and collecting an evaporated liquid of a light phase and a circulating liquid of a heavy phase;
s4, Fenton oxidation treatment: and adding hydrogen peroxide and ferrous sulfate into the evaporated solution to carry out Fenton oxidation reaction, and preparing reaction effluent which can be directly biochemically treated.
Under the action of surfactant, solvent, etc., the resin, pigment and filler in the paint-spraying waste water form a layer of resin colloid coated with hydrated interface film with charges of the same polarity. Therefore, the inorganic acid is added into the paint spraying wastewater, and a large amount of charged ions generated by the ionization of the inorganic acid are utilized to neutralize the charges on the surface of the resin colloid, so that the resin colloid is aggregated and precipitated, and the precipitate is removed by filtering to obtain a first solution. And adding inorganic base into the first solution to neutralize the acidity of the solution, adding inorganic salt, adding the inorganic salt to enhance the polarity of the solution system so as to reduce the solubility of non-polar molecules such as esters, ethers and other organic matters in water, separating out the organic matters in the solution, standing for layering, and separating out the organic matters to obtain a second solution. And then, separating inorganic salt from the solution in the second solution by reduced pressure evaporation to obtain an evaporated liquid and a circulating liquid, and finally adding hydrogen peroxide and ferrous sulfate into the evaporated liquid for Fenton oxidation to oxidize and decompose the residual organic matters in the evaporated liquid.
Preferably, in the step S1, the pH is adjusted to 0 to 4 in the step S1, and the inorganic acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
Further preferably, in the step S1, the heating temperature is 40 to 80 ℃.
Preferably, in step S2, when the inorganic base is sodium hydroxide, the inorganic salt is at least one of sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium nitrate and sodium phosphate; when the inorganic base is potassium hydroxide, the inorganic salt is at least one of potassium carbonate, potassium bicarbonate, potassium chloride, potassium sulfate, potassium nitrate and potassium phosphate; when the inorganic base is calcium hydroxide and/or calcium oxide, the inorganic salt is calcium chloride and/or calcium nitrate, and the inorganic acid is hydrochloric acid and/or nitric acid; when the inorganic base is magnesium hydroxide and/or magnesium oxide, the inorganic salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, and the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid. And adding the inorganic base to adjust the pH of the first reaction liquid to be neutral. The inorganic base is added to neutralize the excess H in the acid precipitation treatment of step S2+And is convenient for the subsequent salting-out treatment by adding inorganic salt.
The specific correspondence between the inorganic acid, the inorganic base and the inorganic salt is shown in the following table:
according to the principle of similar compatibility, the polar solvent is easy to dissolve polar solute, and the nonpolar and weak polar solutes are easy to dissolve in nonpolar and weak polar solvents, so that the polar solvent or the solution containing strong polar solute is added into the reaction solution, the polarity of the aqueous solution system can be enhanced, the solubility of nonpolar molecules in the solution is reduced, and the nonpolar molecules are separated out from the solvent and removed by standing and layering separation. Specifically, add be the saturated inorganic salt solution in the first solution, for water, saturated inorganic salt solution polarity is bigger than water, can effectual improvement aqueous phase's ionic strength, is favorable to the separation of aqueous phase and organic phase, suppresses the formation of emulsion layer, and partial organic matter distributes the proportion at aqueous phase and organic phase interphase simultaneously is little, through adding inorganic salt, can make this type of organic matter distribute more in organic phase, more is favorable to the two-phase layering.
Preferably, the mass fraction of the inorganic salt is 15% to 35%,
preferably, in the step S2, the standing time is not less than 2 h.
Preferably, in the step S3, the circulating liquid is added again to the step S2 to perform the repeated circulating process.
Preferably, the dosage of the ferrous sulfate and the hydrogen peroxide is determined by the COD of the evaporated liquor.
Preferably, in step S4, the mass fraction of the ferrous sulfate is 0.5%, and the mass fraction of the hydrogen peroxide is 2.5% to 25%.
In conclusion, the invention has the following beneficial effects:
firstly, the treatment process adopted by the invention produces less slag, and reduces secondary pollution to the environment.
Secondly, the inorganic salt used in the reduced pressure evaporation treatment in the step S3 of the invention can be added into the step S2 again for recycling, so that the treatment cost is greatly reduced.
Thirdly, the method adopted by the invention has good effect of removing resin and solvent in the wastewater, the final treated effluent has the characteristics of low organic matter concentration, good biodegradability and the like, the biochemical treatment can be directly carried out without dilution, and the organic load of a biochemical treatment system is low.
And fourthly, the saturated inorganic salt solution is used, the polarity of the solution is further increased, the formation of an emulsion layer is inhibited, meanwhile, the distribution ratio of partial organic matters between the water phase and the organic phase is not large, and the organic matters can be distributed more in the organic phase by adding the inorganic salt, so that the two-phase layering is facilitated.
Drawings
FIG. 1 is a schematic view showing the steps of the method for treating the painting waste water according to the first embodiment.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The paint spraying waste water obtained in the following examples of the invention has a pH of 8, a mass of 1000g, a COD of 105000mg/L, a B/C value of 0.09 and a total salt content of 10 g/L.
Example 1
As shown in fig. 1, S1, acid precipitation treatment: adjusting the pH value of the paint spraying wastewater to 0 by sulfuric acid in the paint spraying wastewater, heating to 60 ℃ for reaction, and filtering after the reaction is finished to obtain a first solution;
s2, salting out treatment: adding sodium hydroxide into the first reaction solution to adjust the pH value to 7, then adding 35 wt% of sodium carbonate, stirring and dissolving at 35 ℃, standing for 2 hours, removing an upper organic phase separated out by the solvent, and collecting a lower aqueous phase to obtain a second solution;
s3, reduced pressure evaporation treatment: carrying out reduced pressure evaporation treatment on the second solution, wherein the evaporation capacity is 40 wt%, collecting the evaporated liquid of the light phase and the circulating liquid of the heavy phase, and adding the circulating liquid into the salting-out treatment of the step S2 again for circulating treatment;
s4, Fenton oxidation treatment: 2.5 wt% of hydrogen peroxide with the mass concentration of 30% and 0.5 wt% of ferrous sulfate are added into the evaporated liquor for oxidation reaction, and reaction effluent capable of being directly biochemically treated is prepared.
The paint spraying waste water contains a large amount of resin and solvent, and a small amount of pigment, filler and surfactant, the resin, the pigment and the filler in the solution form a resin colloid which is coated with a layer of hydrated interface film with like charges under the action of the surfactant, the solvent and the like, and the resin colloid can not be mutually bonded, aggregated and precipitated due to mutual repulsion of the like charges. Therefore, the object of the acid precipitation treatment of step S1 of the present invention is to neutralize the charge on the surface of the resin colloid in the solution by adding an inorganic acid to the painting waste water, neutralizing the charge on the surface of the resin colloid with a large amount of charged ions generated by ionization of the inorganic acid, thereby causing the resin colloid to aggregate and precipitate, and then removing the precipitate by filtration to obtain the first solution.
In step S2 of the present invention, an inorganic base is added to the first solution to neutralize excess H in the solution+And is convenient for the subsequent salting-out treatment by adding inorganic salt. According to the similar compatibility principle, the mutual solubility of the polar solvent and the weak polar solvent is high, the polar solvent is easy to dissolve polar solute, and the nonpolar and weak polar solutes are easy to dissolve nonpolar and weak polar solvents, so that the polar solvent or the solution containing the strong polar solute is added into the solution, the polarity of an aqueous solution system can be enhanced, the solubility of the nonpolar molecular ester, ether and other organic solutes in the solution in water is reduced, the nonpolar molecular ester, ether and other organic solutes are separated out of the solution, and the nonpolar molecular ester, ether and other organic solutes are removed by standing and layering separation; specifically, the saturated inorganic salt solution is added into the first solution, and compared with water, the saturated inorganic salt solution has larger polarity, so that the ionic strength of the water phase can be effectively improved, the separation of the water phase and the organic phase is facilitated, the formation of an emulsion layer is inhibited, meanwhile, the distribution ratio of partial organic matters between the water phase and the organic phase is not large, more organic matters are distributed in the organic phase by adding the inorganic salt, the two-phase layering is facilitated, and the step S2 is finished to obtain the second solution.
And then, in the step S3, separating the inorganic salt and the solution in the second solution through reduced pressure evaporation treatment to obtain an evaporated liquid of a light phase and a circulating liquid of a heavy phase containing the inorganic salt, wherein the inorganic salt obtained in the step can be added into the salting-out treatment of the step S2 again for recycling, and finally, in the step S4, hydrogen peroxide and ferrous sulfate are added into the evaporated liquid for fenton oxidation to oxidize and decompose the residual organic matters in the evaporated liquid, and the reaction effluent can be directly subjected to biochemical treatment.
Example 2
The present embodiment is different from embodiment 1 in that: in step S1, heating to 40 ℃; in step S4, the mass fraction of the added hydrogen peroxide is 6 wt%.
Example 3
The present embodiment is different from embodiment 1 in that: in step S1, heating to 80 ℃; in step S2, the mass fraction of the added sodium carbonate is 25 wt%; in step S4, the mass fraction of hydrogen peroxide added is 10 wt%.
Example 4
The present embodiment is different from embodiment 1 in that: in step S1, the pH is adjusted to 2; in step S2, the mass fraction of the added sodium carbonate is 25 wt%; in step S4, the mass fraction of the hydrogen peroxide added is 11 wt%.
Example 5
The present embodiment is different from embodiment 1 in that: in step S1, adjusting the pH to 4; in step S2, the mass fraction of the added sodium carbonate is 25 wt%; in step S4, the mass fraction of hydrogen peroxide added is 12.5 wt%.
Example 6
The present embodiment is different from embodiment 1 in that: in step S2, the mass fraction of the added sodium carbonate is 15 wt%; in step S4, the mass fraction of hydrogen peroxide added is 25 wt%.
Example 7
The present embodiment is different from embodiment 1 in that: in step S1, the added inorganic acid is hydrochloric acid; in step S2, the inorganic salt added is 25 wt% sodium chloride; in step S4, the mass fraction of the added hydrogen peroxide is 20 wt%.
Example 8
The present embodiment is different from embodiment 1 in that: in step S2, the added inorganic base is potassium hydroxide; the inorganic salt added was 25 wt% potassium carbonate; in step S4, the amount of the key raw materials or the reaction conditions of examples 1 to 8 of the present invention in which the mass fraction of hydrogen peroxide added was 4 wt% are shown in the following table,
COD or B/C detection data of effluent from each step of examples 1-8
The initial COD of the painting waste water obtained in the above embodiment of the invention is 105000mg/L, the B/C value is 0.09, and after the painting waste water is treated by the above treatment method of the invention, the COD of the oxidation effluent water subjected to Fenton oxidation treatment in the final step S4 is less than 3400mg/L, and the B/C value is more than 0.4. The object of the invention is therefore: by the treatment method, the treatment cost of the paint spraying wastewater is greatly reduced, and the treated paint spraying wastewater can be directly subjected to biochemical treatment without dilution, so that the organic load of the whole biochemical system is reduced, and the method has the characteristics of high organic matter removal rate, good biodegradability, low treatment cost and the like. And finally, a coagulant is not added into the paint spraying wastewater for coagulation and precipitation, so that a large amount of waste residues are not generated in the reaction process, secondary pollution to the environment is not caused, and the method has green sustainability.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (9)
1. A method for treating paint spraying wastewater, which is characterized by comprising the following steps:
s1, acid precipitation treatment: adding inorganic acid into the paint spraying wastewater to adjust the pH, heating for reaction, and filtering to obtain a first solution;
s2, salting out treatment: adding inorganic base into the first solution, adjusting the pH value to be neutral, then adding inorganic salt, heating for dissolving, standing for layering, removing an upper organic phase separated out by the solvent, and collecting a lower aqueous phase as a second solution;
s3, reduced pressure evaporation treatment: carrying out reduced pressure evaporation on the second solution, and collecting an evaporated liquid of a light phase and a circulating liquid of a heavy phase;
s4, Fenton oxidation treatment: and adding hydrogen peroxide and ferrous sulfate into the evaporated solution to carry out Fenton oxidation reaction, and preparing reaction effluent which can be directly biochemically treated.
2. The method for treating the paint spraying wastewater according to claim 1, wherein in the step S1, the pH is adjusted to 0 to 4, and the inorganic acid is at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
3. The method for treating paint spraying wastewater according to claim 1, wherein the heating temperature in step S1 is 40 to 80 ℃.
4. The method for treating painting waste water according to claim 1 or 2, wherein in the step S2,
when the inorganic base is sodium hydroxide, the inorganic salt is at least one of sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium nitrate and sodium phosphate;
when the inorganic base is potassium hydroxide, the inorganic salt is at least one of potassium carbonate, potassium bicarbonate, potassium chloride, potassium sulfate, potassium nitrate and potassium phosphate;
when the inorganic base is calcium hydroxide and/or calcium oxide, the inorganic salt is calcium chloride and/or calcium nitrate, and the inorganic acid is hydrochloric acid and/or nitric acid;
when the inorganic base is magnesium hydroxide and/or magnesium oxide, the inorganic salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, and the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
5. The method for treating the paint spraying wastewater according to claim 4, wherein the mass fraction of the inorganic salt is 15 to 35%,
6. the method for treating paint spraying wastewater according to claim 1, wherein the standing time period in the step S2 is not less than 2 hours.
7. The method for treating paint spraying wastewater according to claim 1, wherein in the step S3, the circulating liquid is re-introduced into the step S2 to perform a repeated circulating treatment.
8. The method for treating the painting wastewater according to claim 1, wherein the amounts of the ferrous sulfate and the hydrogen peroxide are determined by COD of the evaporated liquid.
9. The method for treating the paint spraying wastewater according to claim 1, wherein in the step S4, the mass fraction of the ferrous sulfate is 0.5%, and the mass fraction of the hydrogen peroxide is 2.5% -25%.
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| CN114044606A (en) * | 2021-11-01 | 2022-02-15 | 长春一汽综合利用股份有限公司 | Method for treating and comprehensively utilizing water-based paint cleaning waste liquid |
| CN114349282A (en) * | 2022-01-11 | 2022-04-15 | 上海依科绿色工程有限公司 | Circulating wastewater treatment and recycling system and recycling method for water curtain spray room of automobile factory |
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Application publication date: 20210629 |