CN107082526B - Pretreatment method of waste emulsion - Google Patents
Pretreatment method of waste emulsion Download PDFInfo
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- CN107082526B CN107082526B CN201710205207.6A CN201710205207A CN107082526B CN 107082526 B CN107082526 B CN 107082526B CN 201710205207 A CN201710205207 A CN 201710205207A CN 107082526 B CN107082526 B CN 107082526B
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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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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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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- 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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a method for pretreating machining oily waste liquid, which comprises the following steps of firstly, passing the machining oily waste liquid through a grating to remove large-particle pollutants; then, the oil, water and sand are separated by a homogenizing adjusting tank; the separated water phase is subjected to two-stage demulsification to destroy a stable emulsion system, and solid-liquid separation is carried out; adjusting the pH value of the separated supernatant after demulsification, and performing Fenton oxidation; after the Fenton reaction is finished, the pH value is adjusted to carry out precipitation, and the effluent enters a biochemical system. The method for treating the oily waste liquid of the mechanical processing disclosed by the invention has the advantages that the oily waste water of the mechanical processing with high COD directly passes through the simple secondary demulsification and Fenton oxidation processes, the COD content is greatly reduced, the turbidity is obviously reduced, the B/C ratio is obviously improved, and conditions are created for biochemical treatment.
Description
Technical Field
The invention relates to a method for pretreating oily waste liquid of machining by adopting a two-stage demulsification and Fenton oxidation combined treatment process, belonging to the field of industrial wastewater treatment.
Background
In the machining of mechanical devices, the surface temperature of the machined devices rises rapidly, and thus cutting fluids formulated with various functional chemical additives, mineral oils, and the like are used to cool and lubricate tools and workpieces. In the processing process, the temperature of the cutting fluid rises all the time, generally reaches 45-90 ℃, substances such as unsaturated lipids in the cutting fluid are oxidized and decomposed at the moment, biodegradable organic matter components are increased, microorganisms can be greatly increased under the appropriate environmental conditions, and therefore the component composition in the cutting fluid is changed, and the function of the cutting fluid is enabled to lose efficacy. Therefore, in the machining process, the cutting fluid generally needs to be replaced by new fluid after being used for a period of time, and the failed cutting fluid needs to be discharged to the outside, so that waste emulsion is generated.
In recent years, with the development of technology, the usage amount of cutting fluid in the machining industry is increased year by year, and the cutting fluid is easy to deteriorate, has a relatively short service life, and is required to be discharged after being used for a period of time, so that the discharge amount of waste emulsion is increased.
The waste emulsion contains a plurality of components such as oil substances, chemical additives and the like which are difficult to degrade biologically, and if the waste emulsion is directly discharged into natural water without being treated, the oil substances in the water can seriously affect the biological and ecological environment of the water after being accumulated to a certain degree.
The waste emulsion is different from general oily waste water, and contains various oil substances (floating oil, emulsified oil, etc.), various additives (anti-rust additive and extreme pressure additive) which are difficult to biodegrade, and partially residual soluble metals (Fe)2+) Therefore, it is difficult to obtain the desired effect by conventional biochemical treatment methods and single demulsification methods (such as acid precipitation and salt precipitation).
Therefore, an efficient method suitable for treating waste emulsions is in need of discovery.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provides a method for pretreating waste emulsion by adopting a two-stage demulsification and Fenton oxidation combined treatment process so as to effectively treat the waste emulsion and relieve the problem of environmental pollution caused by the waste emulsion.
The invention solves the technical problem and adopts the following technical scheme:
a method for pretreating waste emulsion by adopting a two-stage demulsification and Fenton oxidation combined treatment process comprises the following steps of firstly, passing the waste emulsion through a grating to remove large-particle pollutants; then, the oil, water and sand are separated by a homogenizing adjusting tank; the separated water phase is subjected to two-stage demulsification to destroy a stable emulsion system, and solid-liquid separation is carried out; adjusting the pH value of the separated supernatant after demulsification, and performing Fenton oxidation; after the Fenton reaction is finished, the pH value is adjusted to carry out precipitation, and the effluent enters a biochemical system.
The method specifically comprises the following steps:
(1) the waste emulsion passes through a grating to remove large-particle pollutants;
(2) then introducing the waste emulsion into a homogenizing adjusting tank, and carrying out oil, water and sand three-phase separation on the waste emulsion;
(3) introducing the separated water phase into a mixing and regulating tank 1, and adding CaCl2Performing primary demulsification with PFS;
(4) introducing the demulsified wastewater into a solid-liquid separation device for solid-liquid separation to separate out the generated solid precipitate;
(5) introducing the supernatant obtained by solid-liquid separation into a mixing and regulating tank 2, and adding a composite demulsifier and PAM to perform secondary demulsification;
(6) introducing the demulsified wastewater into a solid-liquid separation device for solid-liquid separation to separate out the generated solid precipitate;
(7) introducing the supernatant obtained by solid-liquid separation into a Fenton reaction tank, adjusting the pH of the solution to 2-4 (preferably to about 3) by using a pH adjusting tank, adding a Fenton reagent, and mechanically stirring for 1-5 hours (preferably about 2 hours);
(8) and (3) adjusting the pH of the solution after the Fenton reaction to 8-10 (preferably to about 9), performing flocculation precipitation, and introducing effluent into a biochemical system for subsequent treatment.
CaCl described in step (3)2And the PFS is added in a form of solution prepared by 1-2 g/L and 1-2 g/L respectively. Preferably, said CaCl2And PFS were added at 1.5g/L and 1.5g/L, respectively.
The composite demulsifier in the step (5) is formed by mixing PAC and PFS in a mass ratio of 1: 2; the adding amount of the composite demulsifier and the PAM is 1-3 g/L and 40-60 mg/L respectively, and the composite demulsifier and the PAM are added in the form of solution. Preferably, the dosage of the composite demulsifier and PAM is 2g/L and 50mg/L respectively.
The Fenton reagent added in the step (7) is ferrous sulfate solid powder and 30% (w/w) H2O2And (3) combining the solutions. Preferably, the mass ratio of the COD in the waste emulsion to the ferrous sulfate solid powder in the fenton reagent added in step (7) is: 100-1000 mg, 1-2 g. The ferrous sulfate solid powder in the Fenton reagent added in the step (7) is mixed with 30% H2O2The mass-volume ratio of the solution is as follows: 1.5-3 g, 3-6 ml.
The grating in the step (1) is a middle grating or a large grating, and aims to remove large-particle substances in water and prevent interference on the subsequent steps.
And (3) the homogenization adjusting tank in the step (2) comprises a hydraulic cyclone combined separation device and a floating circulation oil collector to separate oil, water and sand from the waste emulsion.
And (4) the solid-liquid separation device in the step (4) and the step (6) is an inclined plate sedimentation tank.
Sulfuric acid is added in the step (7) to adjust the pH value, the pH value must be accurately adjusted, iron mud is difficult to precipitate due to too low pH value, and the removal effect on COD is reduced due to too high pH value.
Because the waste emulsion contains high COD, the waste emulsion is demulsified once, so that a good effect cannot be achieved, the treatment load of subsequent structures is obviously increased, and the operation cost is increased. Moreover, the waste emulsion has high COD and low BOD, the biodegradability of the waste water is very low, the B/C ratio in the water needs to be improved through the Fenton process, and the biodegradability of the waste water is increased. Therefore, a treatment process combining secondary demulsification and Fenton is adopted in practical engineering.
The invention adopts the two-stage demulsification and Fenton oxidation combined treatment process, thereby not only greatly reducing COD, but also improving the biodegradability of the wastewater. Through the second grade breakdown of emulsion, fully remove the suspended solid in aquatic and the emulsified oil in aquatic, drop the COD of useless emulsion from 62832mg/L to about 20000mg/L, through fenton oxidation process after, the biodegradability of useless emulsion improves by a wide margin.
The invention has the beneficial effects that:
(1) the method for treating the waste emulsion disclosed by the invention enables the waste emulsion with high COD to directly pass through simple secondary demulsification and Fenton oxidation processes, thereby creating conditions for biochemical treatment;
(2) the proportion of the composite demulsifier is verified by experiments, and a good effect is achieved in the demulsification treatment process of the waste emulsion;
(3) in the method, after Fenton treatment, the COD content of the supernatant after solid-liquid separation is greatly reduced, the turbidity is obviously reduced, the B/C ratio is obviously improved, and the load of a subsequent biochemical device can be greatly reduced;
(4) the method has the advantages of very low treatment cost, simple operation and no secondary pollution.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The used waste emulsion in this example is from certain waste recovery center of xi' an, and the waste liquid is stored in No. 1 holding vessel and No. 2 holding vessel respectively. Wherein, after the No. 1 tank is subjected to mixed oil-water separation, the oil phase is as follows: the oil content was approximately 83643.38 mg/L. Water phase: the oil content is 908.28mg/L, the COD concentration is about 62832mg/L, the turbidity is about 6500NTU, and the pH is about 7.0. After the No. 2 tank is subjected to mixed oil-water separation, the oil phase is as follows: the oil content was approximately 69966.9 mg/L. Water phase: the oil content is 1741mg/L, the COD concentration is about 78336mg/L, the turbidity is about 7100NTU, and the pH is about 7.0.
Example 1
This example treats tank 1 waste emulsion as follows:
(1) enabling the waste emulsion in the tank No. 1 to pass through a middle grating, and removing large granular substances in water;
(2) then introducing the waste emulsion into a homogenizing adjusting tank, and carrying out oil, water and sand three-phase separation on the waste emulsion;
(3) introducing the separated water phase into a mixing and regulating tank 1, and respectively adding 1.5g/L CaCl2And 1.5g/L of Polymeric Ferric Sulfate (PFS) for primary demulsification; CaCl2And polyferric sulfate (PFS) are added in the form of solution.
(4) Introducing the demulsified wastewater into a solid-liquid separation device for solid-liquid separation to separate out the generated solid precipitate;
(5) introducing the supernatant into the mixing and adjusting tank 2 again, and adding a composite demulsifier and PAM to perform secondary demulsification; the composite demulsifier is prepared by mixing PAC (polyaluminium chloride) and PFS (polyaluminium chloride) in a ratio of 1:2, wherein the dosage of the composite demulsifier and PAM (polyacrylamide) is 2g/L and 50mg/L, and the composite demulsifier and PAM are prepared into a solution and added.
(6) Carrying out solid-liquid separation on the demulsified wastewater to separate out the generated solid precipitate;
(7) introducing the supernatant into a Fenton reaction tank, adjusting the pH of the solution to about 3 by using a pH adjusting tank, simultaneously adding a Fenton reagent, and mechanically stirring for about 2 hours; the added Fenton reagent is ferrous sulfate solid powder and 30% H2O2And (3) combining the solutions. The mass ratio of COD in the waste emulsion to ferrous sulfate solid powder is as follows: 800mg:1.5 g; ferrous sulfate solid powder and 30% H2O2The mass-volume ratio of the solution is as follows: 2g, 5 ml.
(8) And adjusting the pH value of the solution after the Fenton reaction to be about 9, performing flocculation precipitation, and introducing effluent into a biochemical system for subsequent treatment.
After the oily waste liquid of No. 1 tank machining is treated by the method of the embodiment, the COD of the effluent is reduced to 20000mg/L, the turbidity is reduced to 200NTU, the biodegradability is greatly improved, and the B/C can be improved to 0.37 from 0.16.
Example 2
This example treats tank 2 waste emulsion as follows:
(1) enabling the waste emulsion in the tank No. 2 to pass through a middle grating, and removing large granular substances in water;
(2) then introducing the waste emulsion into a homogenizing adjusting tank, and carrying out oil, water and sand three-phase separation on the waste emulsion;
(3) introducing the separated water phase into a mixing and regulating tank 1, and respectively adding 1.5g/L CaCl2And 1.5g/L of Polymeric Ferric Sulfate (PFS) for primary demulsification; CaCl2And polyferric sulfate (PFS) are added in the form of solution.
(4) Introducing the demulsified wastewater into a solid-liquid separation device for solid-liquid separation to separate out the generated solid precipitate;
(5) introducing the supernatant into the mixing and adjusting tank 2 again, and adding a composite demulsifier and PAM to perform secondary demulsification; the composite demulsifier is prepared by mixing PAC (polyaluminium chloride) and PFS (polyaluminium chloride) in a ratio of 1:2, wherein the dosage of the composite demulsifier and PAM (polyacrylamide) is 3g/L and 60mg/L, and the composite demulsifier and PAM are prepared into a solution and added.
(6) Carrying out solid-liquid separation on the demulsified wastewater to separate out the generated solid precipitate;
(7) introducing the supernatant into a Fenton reaction tank, adjusting the pH of the solution to about 3 by using a pH adjusting tank, simultaneously adding a Fenton reagent, and mechanically stirring for about 3 hours; the added Fenton reagent is ferrous sulfate solid powder and 30% H2O2And (3) combining the solutions. The mass ratio of COD in the waste emulsion to ferrous sulfate solid powder is as follows: 1000mg:2 g; ferrous sulfate solid powder and 30% H2O2The mass-volume ratio of the solution is as follows: 3g, 6 ml.
(8) And adjusting the pH value of the solution after the Fenton reaction to be about 9, performing flocculation precipitation, and introducing effluent into a biochemical system for subsequent treatment.
After the oily waste liquid of No. 2 tank machining is treated by the method of the embodiment, the COD of the effluent is reduced to 20000mg/L, the turbidity is reduced to 210NTU, meanwhile, the biodegradability is greatly improved, and the B/C can be improved to 0.37 from 0.13.
Claims (6)
1. A method for pretreating oil-containing waste emulsion in mechanical processing by adopting a two-stage demulsification and Fenton oxidation combined treatment process is characterized by comprising the following steps of: firstly, the waste emulsion passes through a grating to remove large-particle pollutants; then, the oil, water and sand are separated by a homogenizing adjusting tank; the separated water phase is subjected to two-stage demulsification to destroy a stable emulsion system, and solid-liquid separation is carried out; adjusting the pH value of the separated supernatant after demulsification, and performing Fenton oxidation; after the Fenton reaction is finished, adjusting the pH value for precipitation, and enabling the effluent to enter a biochemical system; comprises the following steps:
(1) the waste emulsion passes through a grating to remove large-particle pollutants;
(2) then introducing the waste emulsion into a homogenizing adjusting tank, and carrying out oil, water and sand three-phase separation on the waste emulsion;
(3) introducing the separated water phase into a mixing and regulating tank 1, and adding CaCl2Performing primary demulsification with PFS;
(4) carrying out solid-liquid separation on the demulsified wastewater to separate out the generated solid precipitate;
(5) introducing the supernatant obtained by solid-liquid separation into a mixing and regulating tank 2, and adding a composite demulsifier and PAM to perform secondary demulsification;
(6) carrying out solid-liquid separation on the demulsified wastewater to separate out the generated solid precipitate;
(7) introducing the supernatant obtained by solid-liquid separation into a Fenton reaction tank, adjusting the pH of the solution to 2-4 by using a pH adjusting tank, adding a Fenton reagent, and mechanically stirring for 1-5 hours;
(8) and adjusting the pH value of the solution after the Fenton reaction to 8-10, performing flocculation precipitation, and introducing the effluent into a biochemical system for subsequent treatment.
CaCl described in step (3)2The adding amount of the PFS is 1-2 g/L and 1-2 g/L respectively, and the PFS is added in a form of preparing a solution;
the composite demulsifier in the step (5) is formed by mixing PAC and PFS in a mass ratio of 1: 2; the adding amount of the composite demulsifier and the PAM is 1-3 g/L and 40-60 mg/L respectively, and the composite demulsifier and the PAM are added in the form of solution.
2. The method of claim 1, wherein: the CaCl is2And PFS were added at 1.5g/L and 1.5g/L, respectively.
3. The method of claim 1, wherein: the dosage of the composite demulsifier and PAM is 2g/L and 50mg/L respectively.
4. The method of claim 1, wherein: the Fenton reagent added in the step (7) is ferrous sulfate solid powder and 30% H2O2And (3) combining the solutions.
5. The method of claim 4, wherein: the mass ratio of COD in the waste emulsion to ferrous sulfate solid powder in the Fenton reagent added in the step (7) is as follows: 100-1000 mg, 1-2 g.
6. The method of claim 4, wherein: the ferrous sulfate solid powder in the Fenton reagent added in the step (7) is mixed with 30% H2O2The mass-volume ratio of the solution is as follows: 1.5-3 g, 3-6 ml.
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| CN110540315A (en) * | 2018-05-28 | 2019-12-06 | 宝山钢铁股份有限公司 | Method and system for pretreating waste emulsion |
| CN108793497B (en) * | 2018-06-27 | 2021-02-02 | 泰山玻璃纤维邹城有限公司 | Method for reducing COD value of waste liquid of glass fiber impregnating compound by chemical method |
| CN109111032B (en) * | 2018-08-29 | 2021-07-16 | 洛阳昊海环保科技有限公司 | Process method for recycling waste emulsion |
| CN109231722B (en) * | 2018-11-16 | 2021-10-29 | 郑州轻工业学院 | Method for treating emulsified oil wastewater in mechanical processing |
| CN110451682A (en) * | 2019-07-31 | 2019-11-15 | 天津大学 | A kind of method that advanced oxidation handles high COD emulsification preparation waste water |
| CN110526494A (en) * | 2019-08-07 | 2019-12-03 | 四川绿艺华福石化科技有限公司 | A kind of processing method of waste emulsified mixture |
| TWI705942B (en) * | 2019-09-17 | 2020-10-01 | 崑山科技大學 | Oil-containing wastewater treatment method and equipment with creating and saving energy efficiency |
| CN111892233A (en) * | 2019-12-27 | 2020-11-06 | 深圳市宝安东江环保技术有限公司 | Method for treating waste emulsion |
| CN112759199A (en) * | 2021-01-13 | 2021-05-07 | 湖北爱国环保技术开发有限公司 | Treatment process of waste cutting fluid |
| CN113697993A (en) * | 2021-08-30 | 2021-11-26 | 衢州华友钴新材料有限公司 | Method for removing oil and reducing COD (chemical oxygen demand) of hydrometallurgy sodium sulfate wastewater |
| CN114477527A (en) * | 2022-01-14 | 2022-05-13 | 广东闻扬环境科技有限公司 | Workshop cleaning wastewater treatment method and system |
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|---|---|---|---|---|
| CN102050532A (en) * | 2009-11-02 | 2011-05-11 | 上海安洁士石油技术有限公司 | Integral treatment process of oily sewage of oil field |
| CN102276072A (en) * | 2010-06-11 | 2011-12-14 | 江苏贝斯特水处理科技有限公司 | Method for treating alkaline oily wastewater with demulsifier |
| EP2784031A1 (en) * | 2013-03-25 | 2014-10-01 | Efacec Engenharia E Sistemas, S.A. | Method of treating leachate, phototreatment reactors and respective use |
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