CN107572685B - Treatment device and method for high-concentration waste emulsion - Google Patents
Treatment device and method for high-concentration waste emulsion Download PDFInfo
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- CN107572685B CN107572685B CN201710774477.9A CN201710774477A CN107572685B CN 107572685 B CN107572685 B CN 107572685B CN 201710774477 A CN201710774477 A CN 201710774477A CN 107572685 B CN107572685 B CN 107572685B
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- 239000002699 waste material Substances 0.000 title claims abstract description 96
- 239000000839 emulsion Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 82
- 238000003860 storage Methods 0.000 claims abstract description 69
- 239000010802 sludge Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 24
- 238000005273 aeration Methods 0.000 claims description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 238000007790 scraping Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 238000005188 flotation Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002173 cutting fluid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009300 dissolved air flotation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007785 strong electrolyte Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to the technical field of water treatment, in particular to a device and a method for treating high-concentration waste emulsion. The treatment device comprises a demulsification precipitation container, an air floatation container and a sludge storage container, wherein a first upper outlet of the demulsification precipitation container is connected with an inlet of the air floatation container, a lower outlet of the air floatation container is connected with an inlet of the demulsification precipitation container, and a lower outlet of the demulsification precipitation container is connected with the sludge storage container.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a device and a method for treating high-concentration waste emulsion.
Background
For a long time, the water pollution in China is serious, along with the development of economy, the discharge amount of industrial wastewater is increased, wherein the emulsion wastewater is one of industrial wastewater with larger yield and mainly comes from industries such as mechanical processing, automobiles, petrochemical industry, steel cold rolling and the like. The emulsion is prepared by diluting emulsified oil with water and adding emulsifier and other additives, and features stable chemical nature, high content of impurities and high Chemical Oxygen Demand (COD). The discharge of the waste emulsion into water can seriously affect the normal growth of aquatic organisms, so that water body pollution is caused, and in addition, organic additives such as alcohol amine substances in the waste emulsion can seriously harm human health through a food chain.
The current method for treating the waste emulsion mainly comprises the following steps:
(1) Sedimentation method: the gravity separation of the two phases is the most basic method in wastewater treatment, and is suitable for wastewater with large density difference between the water phase and the oil phase, and an oil separation tank is a common treatment facility. The method has low operation cost, but with wider and wider research of the emulsifier, better quality and more stable combination of oil and water, so the sedimentation method has poorer and worse effect.
(2) Air floatation method: the combination of the micro bubbles and the oil particles reduces the density of the oil particles and floats to the water surface, thereby realizing oil-water separation. The method has the advantages of wide application range, relatively mature process and good separation effect, but generates a large amount of tiny bubbles in operation, and has high cost, large occupied area and poor treatment efficiency on emulsion with low oil content.
(3) Demulsifier method: according to the interfacial properties of the emulsified oil and the emulsifier in the waste liquid, a demulsifier of a corresponding type is added, and the interfacial tension is changed to aggregate surfactant molecules, so that the surfactant molecules are separated from the waste liquid. The key to this process is the selection of the appropriate demulsifier. Because the components of the waste emulsion are complex and changeable, a single demulsifier cannot meet the treatment requirements of various waste liquids, and the application is limited.
(4) Acid precipitation method: by adding inorganic acid into the waste liquid, a large amount of protons are generated, the electric double layer structure of the surface of the oil phase particles is broken, and the oil phase particles are destabilized, coagulated and separated from water. The method generally combines an air floatation method to float the oil phase to the water surface, and oil scraping is carried out for independent treatment. Experiments prove that the acid precipitation method is only effective on part of the emulsion and has low practicability.
Disclosure of Invention
Aiming at the defects of small range, poor effect and the like of the existing single technology for treating the waste emulsion, the invention provides a device and a method for treating the high-concentration waste emulsion.
According to one aspect of the invention, a treatment device for high-concentration waste emulsion is provided, which comprises a demulsification precipitation vessel, an air floatation vessel and a sludge storage vessel, wherein a first upper outlet of the demulsification precipitation vessel is connected with an inlet of the air floatation vessel, a lower outlet of the air floatation vessel is connected with an inlet of the demulsification precipitation vessel, and a lower outlet of the demulsification precipitation vessel is connected with the sludge storage vessel.
According to one embodiment of the present invention, the treatment apparatus according to the present invention further comprises a waste emulsion storage vessel, a first feed pump, a second feed pump, a third feed pump, a first sludge pump, a second sludge pump, a first effluent storage vessel, a second effluent storage vessel, an oxidation reaction vessel, a sludge storage vessel;
the waste emulsion storage container is connected with the demulsification precipitation container through a first feed pump, the demulsification precipitation container is divided into three paths at an outlet of the demulsification precipitation container, a second upper outlet of the demulsification precipitation container is connected with an inlet of the oxidation reaction container through a first water outlet storage container, and an upper outlet of the oxidation reaction container is connected with a second water outlet storage container; the first upper outlet of the demulsification precipitation container is connected with the inlet of the air floatation container through the second feed pump, and the lower outlet of the air floatation container is connected with the inlet of the demulsification precipitation container through the third feed pump; the lower outlet of the demulsification precipitation container is connected with a sludge storage container through a first sludge pump; the lower outlet of the oxidation reaction container is sequentially connected with a sludge storage container through a second sludge pump; the upper outlet of the air floatation container is connected with the oil sludge storage container.
According to one embodiment of the invention, the outlet of the second effluent storage vessel is also connected to the inlet of the oxidation reaction vessel by a valve.
According to one embodiment of the invention, the treatment device further comprises a biochemical treatment device, and the second effluent storage device is connected to the biochemical treatment device.
According to one embodiment of the invention, the demulsification and precipitation vessel is provided with a pH on-line monitor and a stirrer, and is further provided with a first alkali feeding pump, a first acid feeding pump, an inorganic salt feeding pump, an inorganic flocculant feeding pump and a first organic flocculant feeding pump.
According to one embodiment of the invention, the oxidation reaction vessel is provided with a pH on-line monitor, and is also provided with a second acid feeding pump, an iron sulfate feeding pump and H 2 O 2 A feed pump, a second alkali feed pump, and a second organic flocculant feed pump.
According to one embodiment of the invention, the air flotation container is suspended with an oil scraping device on the liquid surface of the waste emulsion. According to an embodiment of the present invention, the oil scraping device may be an oil scraping plate.
According to one embodiment of the invention, a microporous blasting device is arranged in the air floatation container.
According to another aspect of the present invention, there is provided a method for treating a high concentration waste emulsion, comprising the steps of:
(1) Aeration air floatation degreasing: in the air floatation container, aerating to float the oil phase in the waste emulsion and removing the oil phase;
(2) Demulsification precipitation: and (3) adding inorganic salt into the waste emulsion subjected to the oil removal in the step (1) to demulsify, and then sequentially adding an inorganic flocculant and an organic flocculant to perform flocculation precipitation.
According to one embodiment of the invention, after step (2), the following steps are further included:
(3) Adjusting the pH value: regulating the pH value of the effluent after demulsification and precipitation in the step (2) to 1-6;
(4) Oxidizing: oxidizing the supernatant of the treated waste emulsion;
(5) Precipitation: adding alkaline substances into the waste emulsion subjected to the oxidation treatment, and then adding an organic flocculant for precipitation;
(6) The supernatant obtained after the precipitation in the step (5) is directly discharged or discharged after biochemical treatment.
According to one embodiment of the invention, the method further comprises the step (i) before the aeration air floatation degreasing: the pH of the waste emulsion is adjusted to 1 to 5, preferably to 2 to 3, with a strong acid. Stirring is carried out when strong acid is added, the stirring time is 5-10 minutes, and the stirring speed is 100-300 r/min. The strong acid may be selected from sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid, for example, because the addition amount of the strong acid is small, the introduced system impurities are small, and the processing load of the system is not increased.
According to one embodiment of the present invention, in the step (1), when aeration is performed in the air floatation vessel by using the microporous aeration device, the aeration aperture is 0.1 to 100 μm, and the aeration time is 30 to 60 minutes. Dissolved air flotation may also be used.
When the microporous aeration device is adopted for aeration, the microporous aeration device is arranged at the bottom of the air floatation container, oil content is enabled to float to the liquid level through tiny bubbles generated by the microporous aeration device, and then the oil scraping device suspended on the liquid level of waste liquid of the air floatation container is adopted for oil scraping.
When the dissolved air flotation method is adopted, air in the air compression tank is led into the air flotation container, so that oil content floats up to the liquid level, and then an oil scraping device suspended on the liquid level of waste liquid in the air flotation container is adopted for oil scraping.
According to one embodiment of the invention, the method further comprises the step (ii) after the aeration air floatation degreasing and before demulsification precipitation: the pH of the waste emulsion is adjusted to 5 to 9, preferably to 5 to 8, for example 5, 6, 7 or 8, with a strong base. The strong alkali can be sodium hydroxide, potassium hydroxide or calcium hydroxide, for example, the addition amount of the strong alkali is small, the introduced system impurities are small, and the system treatment load is not increased.
According to an embodiment of the present invention, in step (2), the inorganic salt is selected from strong electrolyte inorganic salts such as calcium chloride, calcium hypochlorite, calcium oxide, magnesium chloride or magnesium sulfate, preferably from calcium chloride; when calcium chloride is selected for demulsification, the demulsification effect is better. The inorganic flocculant is selected from polyaluminum chloride (PAC), polymeric Ferric Sulfate (PFS) or Polymeric Aluminum Ferric Chloride (PAFC); the organic flocculant is selected from Anionic Polyacrylamide (APAM), cationic Polyacrylamide (CPAM) or Nonionic Polyacrylamide (NPAM). According to one embodiment of the invention, the inorganic flocculant is selected from the group consisting of polyaluminum chloride (PAC) and the organic flocculant is selected from the group consisting of Anionic Polyacrylamide (APAM).
According to one embodiment of the invention, in step (2), the inorganic salt is added in an amount of 0.01% to 5%, preferably 0.01% to 3%, such as 0.05%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% by weight of the starting waste emulsion; adding inorganic salt, stirring for 5-10 min at 50-300 r/min, preferably 100-300 r/min, such as 100r/min, 120r/min, 150r/min, 200r/min, 250r/min, 300r/min; the inorganic flocculant is added in an amount of 0.01% to 5%, preferably 0.01% to 3%, for example 0.05%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% by weight of the starting waste emulsion; the addition amount of the organic flocculant is 0.01 to 5 per mill, preferably 0.01 to 3 per mill, for example 0.05 per mill, 0.5 per mill, 1 per mill, 1.5 per mill, 2 per mill, 2.5 per mill and 3 per mill.
According to one embodiment of the invention, in step (2), after adding the inorganic flocculant and the organic flocculant, stirring and clarifying are carried out for 1-10 minutes at a stirring speed of 50-300 r/min, preferably 100-300 r/min, such as 100r/min, 120r/min, 150r/min, 200r/min, 250r/min, 300r/min; the clarification time is 10 to 30 minutes, and may be, for example, 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, 25 minutes, or 30 minutes.
According to one embodiment of the invention, the spent acid is used in step (3) to adjust the pH of the demulsified precipitated effluent to 1-6, preferably to 2-5, such as 2, 3, 4, 5, preferably to 3, in order to provide good conditions for the oxidation reaction. The waste acid is waste liquid with acid as main component, preferably strong acid, such as waste sulfuric acid, waste nitric acid, waste phosphoric acid, waste hydrochloric acid, etc. produced in industrial production, scientific experiment, etc. because the adding amount of strong acid is small, the introduced system impurity is small, and the system treatment load is not increased. Of course, a high-quality acid (i.e., a commercially available acid having a purity of 90% or more and 95% or more, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) may be used.
According to one embodiment of the present invention, the oxidation treatment in the step (4) may be, for example, fenton oxidation, wherein the concentration of ferrous sulfate heptahydrate is 1mol/L, the mass fraction of hydrogen peroxide is 30%, the molar ratio of ferrous sulfate to hydrogen peroxide is 1 (10-50), and the addition amount of the ferrous sulfate and the hydrogen peroxide is determined by the COD of the solution.
According to one embodiment of the invention, the alkaline substance in step (5) is selected from the group consisting of calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, preferably auto-calcium oxide. The alkaline substance is used in an amount of 1g/L to 20g/L based on the weight of the starting waste emulsion. The organic flocculant in step (5) is selected from Anionic Polyacrylamide (APAM), cationic Polyacrylamide (CPAM) or Nonionic Polyacrylamide (NPAM), preferably from Anionic Polyacrylamide (APAM). The organic flocculant is added in an amount of 0.01 to 5 per mill, preferably 0.01 to 3 per mill, for example 0.05, 0.5, 1, 1.5, 2, 2.5 and 3 per mill, based on the weight of the initial waste emulsion.
According to one embodiment of the invention, the biochemical treatment in step (6) is performed using, for example, an A-O tank, a biological contact oxidation tank, or an MBR apparatus, etc.
According to one embodiment of the invention, when COD in the effluent after the oxidation treatment and precipitation is greater than 2000mg/L, the effluent is returned to the oxidation reaction vessel for secondary oxidation.
And (5) carrying out safe burying or incineration treatment on sludge generated in the treatment process.
The invention provides a treatment technology combining acidification air flotation, demulsification precipitation and Fenton oxidation. For the high-concentration waste emulsion, the treatment difficulty is high because the oil and the water are not mutually soluble. The invention firstly uses an acidification air floatation method to float oil particles in the waste emulsion to the surface, and uses an oil scraping device to scrape the oil phase. After the oil phase is removed, strong electrolyte (such as sodium hydroxide and calcium salt) is added into the waste emulsion to realize demulsification. After demulsification, the waste liquid is in a suspension state, and a flocculating agent is added to precipitate suspended matters, so that solid-liquid separation is realized. The supernatant after the precipitation is removed enters an oxidation reaction device for further oxidation, and some organic matters with better solubility are removed. Finally, the effluent reaches the standard or enters a biochemical reaction container for continuous treatment.
The invention has the following beneficial effects:
(1) The method of combined technology is adopted to treat the high-concentration waste emulsion, the advantages of each technology are fully exerted, different types of pollutants in the waste emulsion are treated respectively, the treatment efficiency of each unit is improved, and the operation cost is reduced.
(2) The invention adopts multi-line connection, has flexible process route, independent module units, can timely adjust the treatment scheme according to different properties of specific wastewater, can conveniently carry out reflux treatment when the effluent quality is not ideal, realizes the effective utilization of each process unit, improves the overall efficiency, reduces the cost and expands the application range.
Drawings
FIG. 1 is a schematic view of a treatment apparatus for high concentration waste emulsion according to the present invention;
wherein the waste emulsion storage vessel 1-first feed pump, 3-demulsification precipitation vessel, 4-first sludge pump, 5-sludge storage vessel, 6-first effluent storage vessel, 7-oxidation reaction vessel, 8-second effluent storage vessel, 9-biochemical treatment device, 10-second sludge pump, 11-first valve, 12-second valve, 13-second feed pump, 14-air floatation vessel, 15-third feed pump, 16-oil scraping device, 17-sludge storage vessel, 21-first alkali feed pump, 22-first acid feed pump, 23-inorganic salt feed pump, 24-inorganic flocculant feed pump, 25-first organic flocculant feed pump, 31-second acid feed pump, 32-iron sulfate feed pump, 33-H 2 O 2 The device comprises a feed pump, a 34-second alkali feed pump, a 35-second organic flocculant feed pump, a-waste emulsion, a second upper outlet of a b-demulsification precipitation container, a first upper outlet of a c-demulsification precipitation container, a lower outlet of a d-demulsification precipitation container, an upper outlet of an e-air floatation container, a lower outlet of an f-air floatation container, an upper outlet of a g-oxidation reaction container and a lower outlet of an h-oxidation reaction container.
Detailed Description
The present invention is described in detail in the following description, which is not to be construed as limiting the invention.
As shown in fig. 1, the treatment apparatus for high concentration waste emulsion according to the present invention comprises a demulsification and precipitation vessel 3, an air flotation vessel 14 and a sludge storage vessel 5, wherein a first upper outlet c of the demulsification and precipitation vessel 3 is connected with an inlet of the air flotation vessel 14, a lower outlet f of the air flotation vessel 14 is connected with an inlet of the demulsification and precipitation vessel 3, and a lower outlet d of the demulsification and precipitation vessel 3 is connected with the sludge storage vessel 5.
The treatment device according to the present invention further comprises a waste emulsion storage vessel 1, a first feed pump 2, a second feed pump 13, a third feed pump 15, a first sludge pump 4, a second sludge pump 10, a first effluent storage vessel 6, a second effluent storage vessel 8, an oxidation reaction vessel 7, and an oil sludge storage vessel 17;
the waste emulsion storage container 1 is connected with the demulsification precipitation container 3 through the first feed pump 2, the demulsification precipitation container 3 is divided into three paths at the outlet, the second upper outlet b of the demulsification precipitation container 3 is connected with the inlet of the oxidation reaction container 7 through the first effluent storage container 6, and the upper outlet g of the oxidation reaction container 7 is connected with the second effluent storage container 8; the first upper outlet c of the demulsification and precipitation container 3 is connected with the inlet of the air floatation container 14 through the second feeding pump 13, and the lower outlet f of the air floatation container 14 is connected with the inlet of the demulsification and precipitation container 3 through the third feeding pump 15; the lower outlet d of the demulsification precipitation vessel 3 is connected with a sludge storage vessel 5 through a first sludge pump 4; the lower outlet h of the oxidation reaction vessel 7 is sequentially connected with the sludge storage vessel 5 through a second sludge pump 10; the upper outlet e of the air floating container 14 is connected with the sludge storage container 17.
In the apparatus for treating a high concentration waste emulsion according to the present invention, the outlet of the second effluent storage vessel 8 is further connected to the inlet of the oxidation reaction vessel 7 through a first valve 11.
The treatment device for high concentration waste emulsion according to the present invention further comprises a biochemical treatment device 9, and the second effluent storage device 8 is connected to said biochemical treatment device 9, for example by means of a second valve 12. The biochemical treatment device is selected from an A-O tank, a biological contact oxidation tank, an MBR device, and the like.
The demulsification precipitation vessel 3 can be provided with a pH on-line monitor and a stirrer, and is also provided with a first alkali feeding pump 21, a first acid feeding pump 22, an inorganic salt feeding pump 23, an inorganic flocculant feeding pump 24 and a first organic flocculant feeding pump 25.
The oxidation reaction vessel can be provided with a pH on-line monitor, and is also provided with a second acid feeding pump 31, an iron sulfate feeding pump 32 and H 2 O 2 A feed pump 33, a second base feed pump 34, a second organic flocculant feed pump 35.
The air flotation vessel 14 has a wiper 16 suspended above the waste emulsion level (the level is shown in phantom in fig. 1).
A microporous gas explosion device can also be arranged in the air floatation container 14.
The first alkali feed pump, the first acid feed pump, the inorganic salt feed pump, the inorganic flocculant feed pump and the first organic flocculant feed pump which are respectively independent and are arranged in the demulsification and precipitation vessel according to the invention can carry out the steps (i), (ii) and (2) in the demulsification and precipitation vessel, and the specific processes are as follows: after the waste emulsion enters a demulsification and precipitation container through a waste emulsion storage container and a first feed pump, firstly, only a first acid feed pump is turned on to adjust the pH of the waste emulsion to 1-5 (step (i)), then the waste emulsion enters an air floatation container through a second feed pump to carry out aeration air floatation oil removal, then the waste emulsion returns to the demulsification and precipitation container through a third feed pump, at the moment, only a first alkali feed pump is turned on to adjust the pH of the waste emulsion to 5-9 (step (ii)), then an inorganic salt feed pump is turned on to add inorganic salt into the waste emulsion for demulsification, and then an inorganic flocculant feed pump and a first organic flocculant feed pump are sequentially turned on to add inorganic flocculant and organic flocculant for flocculation and precipitation (step (2)).
In the present invention, the opening and closing of each feed pump may be controlled by, for example, a valve, for example, opening and closing the second upper outlet and the first upper outlet of the demulsification and precipitation vessel.
In the invention, the "high-concentration waste emulsion" means that the waste emulsion to be treated has a higher oil content. For example, when the waste liquid to be treated is detected by an oil meter, the oil content therein is 5% or more, even 10% or more, for example, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12% or more, or the like by weight. When the waste emulsion to be treated contains a high oil content (the oil content is 5% or more by weight, or even 10% or more by weight), the COD is high, the specific gravity is high, and the solution is black, blackish brown, grey, yellow or yellowish brown, etc. At this time, it is often necessary to perform two demulsification steps: one time is demulsification air floatation oil removal, and one time is demulsification precipitation.
In the present invention, the "container" in the "waste emulsion storage container" may be a reaction tank, or the like for containing a reactant and providing a reaction site, and the same meaning as the "container" in the "demulsification precipitation container", "sludge storage container", "effluent storage container", "oxidation reaction container", "biochemical treatment apparatus", "air floatation container", and "sludge storage container" should be taken as well.
In the invention, a first feed pump is used for pumping waste emulsion from a waste emulsion storage container into a demulsification precipitation container; the second feed pump is used for pumping the waste emulsion from the demulsification precipitation container into the air floatation container; the third feed pump is used for pumping the waste emulsion back to the demulsification precipitation container from the air floatation container; the first sludge pump is used for pumping the sediment/sludge obtained after flocculation and precipitation in the demulsification sediment container into the sludge storage container; the second sludge pump is used for pumping the sludge obtained after the oxidation reaction in the oxidation reaction container into the sludge storage container; the first effluent storage container is used for storing the waste emulsion obtained after demulsification and precipitation reaction; the second effluent storage container is used for storing the waste emulsion obtained after the oxidation reaction; the oil sludge storage container is used for storing the oil collected by the oil scraping device after aeration and air floatation; the sludge storage vessel is used for storing sediment/sludge generated by demulsification precipitation reaction and oxidation reaction.
The method for treating the high-concentration waste emulsion of the present invention will be described with reference to specific examples.
Example 1
The waste emulsion in this example was taken from a cutting fluid from a plant in a Shijia, and Table 2 shows water quality detection index data of the cutting fluid from a Shijia.
TABLE 2 Water quality detection index data for certain cutting fluids of Shijia
Certain cutting fluid for Shijia has high oil content, high specific gravity and high COD, and the solution is black brown.
The waste emulsion to be treated is led into a waste emulsion storage container and then enters a demulsification precipitation container through a feed pump. Under stirring (stirring time is 5 minutes, stirring speed is 250 r/min), adding 68% nitric acid to the demulsification precipitation vessel by a first acid feed pump until the pH of the waste cutting fluid is about 3. Then sequentially passing through a first upper outlet and a second feeding pump of the demulsification precipitation container, and entering an air floatation container for aeration air floatation, wherein the aeration aperture is 50 mu m, and the aeration time is 30 minutes. Oil is collected by an upper outlet of the air floatation container through an oil scraping device and enters an oil sludge storage container, and waste emulsion is returned to the demulsification precipitation container through a third feed pump from a lower outlet of the air floatation container.
Adding calcium hydroxide into the demulsification precipitation container by a first alkali feeding pump until the pH value of the solution is about 7, adding 0.1% of calcium oxide by an inorganic salt feeding pump, stirring at the speed of 100r/min for 8 min, sequentially opening an inorganic flocculant feeding pump and a first organic flocculant feeding pump, firstly adding 0.2% of PAFC into the demulsification precipitation container by the inorganic flocculant feeding pump, then adding 0.2 permillage of APAM into the demulsification precipitation container by the first organic flocculant feeding pump, stirring at the speed of 250r/min for 2 min, and standing for clarifying for 15 min. The obtained supernatant enters the first effluent storage container from the second upper outlet of the demulsification precipitation container for storage, and the obtained precipitate enters the sludge pump from the lower outlet of the demulsification precipitation container and is pumped into the sludge storage container for storage by the sludge pump. The whole demulsification time is about 60 minutes, the COD of the solution is reduced from 102900mg/L to 24605mg/L, and the COD removal rate is 76.1%.
The waste emulsion stored in the first effluent storage vessel is then fed into the oxidation reaction vessel and is pumped by the second acid feed pumpWaste emulsion: and adding waste phosphoric acid into the solution according to the molar ratio of 100:1, regulating the pH value of the solution to 3, and then carrying out Fenton oxidation. The ferrous sulfate heptahydrate is added once by using an iron sulfate charging pump, and the adding amount is 33.36kg relative to each ton of waste emulsion, and H is used 2 O 2 The feeding pump is used for feeding 30% hydrogen peroxide in three times, and the feeding amount of the feeding pump is 200L/t, 60L/t and 40L/t in sequence relative to each ton of waste emulsion. After 3 hours of reaction, calcium oxide is added by using a second alkali feeding pump, the pH value of the waste emulsion is adjusted to 9, and the adding amount is 17kg for each ton of waste emulsion; and then adding CPAM by using a second organic flocculant feed pump to perform flocculation precipitation, wherein the adding amount is 0.03kg for each ton of waste emulsion. The COD of the solution is reduced from 24605mg/L to 2378mg/L, the COD removal rate is 90.3%, the effluent of the oxidation reaction vessel enters the A-O pool for biochemical treatment through the second effluent storage vessel, and the effluent COD of the biochemical pool is treated<300mg/L, ammonia nitrogen<30mg/L, pH is 6-9, total salt<5000mg/L, and the effluent meets the three-level emission standard of Integrated wastewater discharge Standard (GB 8978-1996).
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The high-concentration waste emulsion treatment device is characterized by comprising a demulsification precipitation container, an air floatation container, a sludge storage container, a first water outlet storage container, a second water outlet storage container and an oxidation reaction container, wherein the outlet of the demulsification precipitation container is divided into three paths, the first upper outlet of the demulsification precipitation container is connected with the inlet of the air floatation container, the lower outlet of the air floatation container is connected with the inlet of the demulsification precipitation container, the second upper outlet of the demulsification precipitation container is connected with the inlet of the oxidation reaction container through the first water outlet storage container, the lower outlet of the demulsification precipitation container is connected with the sludge storage container, and the upper outlet of the oxidation reaction container is connected with the second water outlet storage container;
wherein, be provided with pH on-line monitoring appearance and agitator in the demulsification precipitation container, still be provided with first alkali charge pump, first acid charge pump, inorganic salt charge pump, inorganic flocculant charge pump and first organic flocculant charge pump.
2. The treatment apparatus according to claim 1, further comprising a waste emulsion storage vessel, a first feed pump, a second feed pump, a third feed pump, a first sludge pump, a second sludge pump, a sludge storage vessel;
the waste emulsion storage container is connected with the demulsification precipitation container through a first feed pump; the first upper outlet of the demulsification precipitation container is connected with the inlet of the air floatation container through the second feed pump, and the lower outlet of the air floatation container is connected with the inlet of the demulsification precipitation container through the third feed pump; the lower outlet of the demulsification precipitation container is connected with a sludge storage container through a first sludge pump; the lower outlet of the oxidation reaction container is sequentially connected with a sludge storage container through a second sludge pump; the upper outlet of the air floatation container is connected with the oil sludge storage container.
3. The treatment device according to claim 2, wherein the outlet of the second effluent storage vessel is further connected to the inlet of the oxidation reaction vessel by a valve.
4. The treatment device of claim 2, further comprising a biochemical treatment device, and wherein the second effluent storage device is coupled to the biochemical treatment device.
5. The treatment device according to claim 2, wherein the oxidation reaction vessel is provided with a pH on-line monitor, and is further provided with a second acid feed pump, an iron sulfate feed pump, and H 2 O 2 A feed pump, a second alkali feed pump, and a second organic flocculant feed pump.
6. The treatment device according to claim 1, wherein the air flotation vessel is suspended with a scraping means above the level of the waste emulsion.
7. The treatment device according to claim 1, wherein a microporous aeration device is provided in the air-float container.
8. A method for treating a high-concentration waste emulsion, which is applied to the high-concentration waste emulsion treatment device according to any one of claims 1 to 7, the method comprising the steps of:
(1) Adjusting the pH value of the waste emulsion to 1-5 by using strong acid;
(2) Aeration air floatation degreasing: in an air floatation container, aerating to float the oil phase in the waste emulsion after the pH value is regulated in the step (1) and removing the oil phase;
(3) Demulsification precipitation: adding inorganic salt into the waste emulsion subjected to the oil removal in the step (2) to demulsify, and then sequentially adding an inorganic flocculant and an organic flocculant to perform flocculation precipitation, wherein the adding amount of the inorganic salt is 0.01% -5% by weight of the initial waste emulsion;
(4) Adjusting the pH value: regulating the pH value of the effluent after demulsification and precipitation in the step (3) to 1-6;
(5) Oxidizing: and (3) oxidizing the supernatant of the treated waste emulsion.
9. The process of claim 8, further comprising the step, after step (5), of:
(6) Precipitation: adding alkaline substances into the waste emulsion subjected to the oxidation treatment in the step (5), and then adding an organic flocculant for precipitation;
(7) The supernatant obtained after the precipitation in the step (6) is directly discharged or discharged after biochemical treatment.
10. The method according to claim 9, wherein the inorganic flocculant is selected from polyaluminum chloride, polyaluminum ferric sulfate or polyaluminum ferric chloride; the organic flocculant is selected from anionic polyacrylamide, cationic polyacrylamide or nonionic polyacrylamide; the adding amount of the inorganic flocculant is 0.01% -5% by weight of the initial waste emulsion, and the adding amount of the organic flocculant is 0.01% -5%.
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| CN109665678A (en) * | 2019-02-25 | 2019-04-23 | 辽宁拓启环保科技有限公司 | A kind of fatty acid production wastewater treatment process |
| CN110563082A (en) * | 2019-09-19 | 2019-12-13 | 中国农业科学院烟草研究所 | Composition for pretreating cutting fluid wastewater and application thereof |
| CN113716812A (en) * | 2021-09-16 | 2021-11-30 | 江苏迈奥环保科技有限公司 | Recycling process of waste emulsion |
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