CN1312048C - Method for treating waste cutting liquid by coupling technique - Google Patents
Method for treating waste cutting liquid by coupling technique Download PDFInfo
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- CN1312048C CN1312048C CNB2004100209827A CN200410020982A CN1312048C CN 1312048 C CN1312048 C CN 1312048C CN B2004100209827 A CNB2004100209827 A CN B2004100209827A CN 200410020982 A CN200410020982 A CN 200410020982A CN 1312048 C CN1312048 C CN 1312048C
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Abstract
The present invention relates to a technology for treating industrial waste water, particularly to a method for treating waste cutting liquid by using a coupling technique. The method comprises the following steps: carrying out air flotation-flocculation treatment firstly with 0.2 to 0.4Mpa of pressure and dosage of flocculating agents equal to 0.1% to 6% of the weight of waste water, carrying out ultrafiltration-reverse osmosis treatment comprising steps of carrying out two-stage micro-membrane filtering on the waste water with 0.05 to 0.6Mpa of operation pressure and carrying out reverse osmosis with 0.5 to 1.5Mpa of operation pressure then, and finally carrying out electricity-heterogeneous catalysis oxidation treatment with 10 to 15V of voltage, 100mA to 400mA per square decimeter of current density, supported catalyst containing active constituents of oxides of Fe or Mn as catalyst and 1.2 to 5 of the ratio of V (the waste water) to V (the catalyst). The present invention has the advantages of good treatment effects, low operating cost and convenient operation, the waste water can be directly discharged and no secondary pollution is generated.
Description
Technical field
The present invention relates to technology for treating industrial waste water, specifically a kind of employing coupling technique processing cutting liquid method for waste water.
Background technology
At present, the water-emulsifiable oil-cutting fluid waste water that some chemical companies produce in process of production contains basal liquid (vegetable and animals oils, mineral oil, synthetic oil), oiliness improver (lipid, lipid acid, higher alcohols), tensio-active agent (negatively charged ion system, nonionic system), rust-preventive agent, anticorrosive agent and other are as defoamer, complexing of metal ion agent, tinting material etc., biodegradability extreme difference.
The air supporting method mainly is to feed or produce a large amount of bubbles in water, form water, gas and be removed material three-phase heterodisperse system, under the effect of interfacial tension, bubble floating power and hydrostaticpressure difference, bubble and the combination that is removed material are floated to the water surface, realize and water sepn.Flocculence is a dosing coagulant in water, destroys water-borne glue body particulate steady state, under certain hydraulics, by mutual collision and the gathering between micelle, thereby form be easy to isolating floss from water (Chen Fu etc., water technology and medicament complete works, P433-435).Two kinds of methods are used in combination, and pollutent is removed, and reach the purpose that purifies water.
The pressure air-dissolving air-float method is that pressure is added to 0.2-0.5MPa, and air dissolves in the waste water, then is dispersed in the water and with the wadding piece by reliever release air formation microbubble to adhere to each other.This method advantage is molten large-minded under the high pressure, and the microbubble that discharges by reliever is fine, epigranular, and intensity is big, and come-up is stable, and is small to the disturbance of liquid, is specially adapted to the loose short grained solid-liquid separation of particulate fines.
Since the seventies, reverse osmosis method was recycled electroplating wastewater, membrane sepn was handled waste water and is used widely.(Xu Zhenliang, embrane method water technology)
Membrane sepn be by film to the chemosmotic difference of each components selection in the mixture, being impellent with outside energy or chemical potential difference separates two-pack or polycomponent blended gas or liquid, classification is purified and the method for enrichment.
The separating mechanism of ultrafiltration is generally also thought sieving action, but its separation is a molecular level, can hold back dissolved macromole solute in the solution, and sees through the small molecules solute.Reverse osmosis is to see through the component selective dissolution in coating materials liquid side, and under film two side static pressure differences promoted, diffusion saw through film then.(Liu Moe, application of membrane separation technology handbook)
Chinese patent (the patent No.: ZL92106153.6) disclose a kind of electric-multiphase catalytic process and reactor thereof, the electric-multiphase catalytic reaction process, be that chemical catalysis and electrocatalysis process are combined, utilize catalyst activity component and electric activated acting in conjunction, make reaction molecular activation, can be than carrying out single reaction that can not take place under the mild reaction conditions with catalyzer.The electric-multiphase catalytic oxidation is at normal temperatures and pressures, under the synergy of electric field and catalyzer, makes larger molecular organics be converted into small molecules or CO
2And water, reduce content of harmful, thereby reach the emission standard of waste water.
Summary of the invention
The object of the present invention is to provide that a kind of treatment effect is good, equipment is simple, working cost is low, the method for non-secondary pollution, the employing coupling technique processing cutting liquid waste water that is suitable for applying.
For achieving the above object, the technical solution used in the present invention is as follows:
At first carry out air supporting-flocculation treatment: its pressure is 0.2～0.4Mpa, and the consumption of flocculation agent is 0.1%～6% of a waste water weight; Carry out ultrafiltration-reverse-osmosis treated again: waste water is carried out the two-stage mocromembrane filter, its operating pressure is 0.05～0.6Mpa, carries out reverse osmosis then, and its operating pressure is 0.5～1.5Mpa; Carry out the electric-multiphase catalytic oxide treatment at last: volts DS is 10～15V between electrode in electric field, electric current is under the extra electric field of every square decimeter of 100mA～400mA, make in the cutting fluid waste water organic pollutant at the catalyst surface catalyzed oxidation, catalyzer is that the oxide compound with Fe or Mn is the loaded catalyst of active ingredient, the content of its active ingredient is 1～4% of total catalyst weight, V
Water: V
Catalyzer=1.2～5.
Described flocculation agent (A agent) is Tai-Ace S 150, ferrous sulfate, polymerize aluminum chloride (promptly poly-aluminium) or bodied ferric sulfate (promptly poly-iron), when flocculation agent is that optimum amount is 1.5% of a waste water weight when gathering aluminium; Can add coagulant aids (B agent) in described air supporting-flocculation treatment process, this coagulant aids is anionic polyacrylamide or cationic polyacrylamide, its usage quantity is 0.001%～0.0025% of a waste water weight, when using molecular weight is anionic polyacrylamide more than 1,400 ten thousand when making coagulant aids, and its optimum quantum of utilization can be reduced to 0.0015% of waste water weight.The A agent is a kind of multinuclear that has, the positively charged ion combination drug of high price electricity, colloidal particle and oil in water emulsion surface charge in being used for and in the waste water, the electrostatic double layer of compression micelle, along with the destruction of electrostatic double layer, the repulsion current potential of oil in water emulsion micelle disappears, and runs foul of each other between the micelle gradually and water sepn; The B agent is the organic high molecular polymer coagulant aids, utilizes the powerful bridge formation and volume continuous cropping usefulness of B agent, forms the bulk flocs unit.By isolated plant (unit effect) waste water is pressurizeed, aerating, dosing, mixing (gas, medicine, water), discharges, make it to take place flotation, precipitation, flocs unit is separated from water body quickly and efficiently, reach the water purifying purpose.
In the described ultrafiltration reverse-osmosis treated process, the filtering first step mocromembrane of two-stage mocromembrane aperture is 5 microns (more greatly), filters macromole, suspended substance, and mocromembrane aperture, the second stage is 0.22 micron, depth type filtration, the anti-pressure ability of film is 0.3～0.6MPa; Exchange capacity of reverse-osmosis treated is 15% for what handle wastewater flow rate, repeatedly circulates; Only otherwise damage mould material (pressure excessive or water film is had severe corrosive), processing efficiency remains unchanged.
Described electric-multiphase catalytic oxide catalyst, the content of its active ingredient are 1～4% of total catalyst weight, V
Waste water: V
Catalyzer=1.2～5, when the content of metal active constituent is 2～3% of total catalyst weight, V
Waste water: V
Catalyzer=3 o'clock, best results;
Described catalyzer can adopt immersion process for preparing: with carrier impregnation in the soluble chloride or nitrate aqueous solution that contain Fe or Mn metal ion; the concentration of its metal salt solution is 0.12～1.0mol/L; solution is 0.8～1.5: 1 with the carrier bulk ratio; after placing 10～24 hours under 25～30 ℃; in 110～130 ℃ of oven dry down, last, in 300～400 ℃; roasting is 4～8 hours under nitrogen protection, can make the purpose catalyzer.
The present invention has following advantage:
1. the cutting fluid waste water that effectively produces in the processing production process of the present invention.Experimental result shows, can reach the pre-treatment purpose with flocculation-ultrafiltration reverse-osmosis treated cutting fluid waste water, passes through the electric-multiphase catalytic effect again, can directly discharge.
2. air supporting in the inventive method-employed medicament that flocculates obtains easily, adds simply, and working cost is cheap relatively, and actual application value is arranged.
3. easy and simple to handle in the film treating processes in the inventive method, operating pressure is low, the processing efficiency height;
4. the electric-multiphase catalytic process operation is easy in the inventive method, and the reaction conditions gentleness is carried out at normal temperatures and pressures, is particularly suitable for handling some intermediate concentration used water difficult to degradate, and working cost is cheap, and equipment is simple, and non-secondary pollution produces.
Embodiment
Embodiment 1
Conventional flocculation agent is to the cutting fluid water treatment effect
Numerical value when flocculating effect is got the flocculation agent optimum amount, the usage quantity of high molecular polymer coagulant aids anionic polyacrylamide is 15mg/L, COD
Cr(mensuration of chemical oxygen demand (COD)) adopts water quality dichromate titration (GB 11914-89) to analyze, and is as follows.
Former water is COD after oil removal is handled
Cr: 76869mg/L, PH:7-8, flocculation the results are shown in Table 1.
The conventional flocculation agent of table 1. is to cutting fluid wastewater treatment best effect
| Flocculation agent | Tai-Ace S 150 (6%) | Ferrous sulfate (6%) | Poly-aluminium (1.5%) | Poly-iron (1.5%) |
| Flocculation back COD Cr (mg/L) * | 13048 | 14857 | 11840 | 13762 |
| Flocculation back COD Cr (mg/L) ** | 14250 | 21048 | 11958 | 11472 |
*The coagulant aids molecular weight that uses is more than 1,400 ten thousand
*The coagulant aids molecular weight that uses is between 4,000,000～5,000,000
Because of the effect of two kinds of coagulant aidss to waste water is more or less the same (just poly-iron difference is big), so use more cheap (molecular weight is more than 1,400 ten thousand) to make coagulant aids in the experiment afterwards.
Embodiment 2
Contrast with the eddy-current method processing efficiency
Under same experiment condition (waste water quality, the water yield is identical with medicament and consumption), use molten air supporting method of total head and eddy-current method that waste water is handled, adopt poly-aluminium to make flocculation agent, consumption is 1.5% of a wastewater flow rate, result sees Table 2.
Molten air supporting method of table 2. total head and eddy-current method contrast the wastewater treatment result
| Method | Flocculation back COD Cr(mg/L) |
| The molten air supporting method of total head | 11840 |
| Eddy-current method | 23050 |
From experimental result, with the molten air supporting method of total head waste water is flocculated, treatment effect is better than eddy-current method.
Embodiment 3
Flocculation agent is to the treatment effect of cutting fluid waste water in the amplification process
After determining to make with medicament, strengthen the flocculation water consumption, the test flocculating effect.From The above results, reach the optimum handling effect, dosing should be 1.5% of wastewater flow rate.
Former water COD
Cr: 76869mg/L, PH:7-8, flocculation the results are shown in Table 4.
The different flocculation agents of table 4. in amplification process to the treatment effect of cutting fluid waste water
| Water sample consumption (ml) | COD behind the addition polymerization aluminium Cr (mg/L) | COD behind the addition polymerization iron Cr (mg/L) |
| 200 | 11174 | 13762 |
| 400 | 11168 | 13269 |
| 800 | 11168 | 13282 |
Embodiment 4
Ultrafiltration and reverse-osmosis treated
Ultra-filtration and separation is filtered for the two-stage mocromembrane: first step aperture is 5 microns (more greatly), filters macromole, suspended substance; Aperture, the second stage is 0.22 micron, depth type filtration, and operating pressure is 0.1MPa.Reverse-osmosis treated, about operating pressure 1MPa, one time exchange capacity is 15%, repeatedly circulation.Two kinds of films are the hollow cellulose film, Tianjin MoTian Membrane Engineering Technology Co., Ltd's product.Model: MOF-905, specification: 90 * 500mm.
After the air supporting processing, COD
Cr: 11415mg/L, PH:6-7, flocculation the results are shown in Table 5.
Table 5. ultrafiltration and reverse-osmosis treated effect
| Reaction times (h) | Reaction back CODcr (mg/L) | Clearance (%) |
| 1 | 382 | 96.6 |
| 2 | 378 | 96.6 |
| 3 | 379 | 96.6 |
| 4 | 382 | 96.6 |
Because cutting fluid waste water is more difficult, COD
CrHeight, through after the pre-treatment, COD
CrDrop to about 400mg/L, can't qualified discharge, continue can handle this strand waste water better by the electric-multiphase catalytic reaction device.
Embodiment 5
The preparation of M/ activated-carbon catalyst:
Get the Fe (NO of 0.36mol/L
3)
3Solution 100ml pours 100 gram mesopore activated carbon particles in the steeping fluid into and to stir, and places 10 hours, dries 2 hours down in 110 ℃, again in 350 ℃ of following roastings 4 hours, naturally cools to room temperature and makes catalyst A.The weight of metal component is in the catalyst A: Fe:2%, all the other are carrier active carbon.
Similarity condition is made the weight catalyst B of metallic components Mn.
Embodiment 6
Electric-multiphase catalytic for pretreated cutting fluid waste water is tested I continuously
In the electric-multiphase catalytic reaction device that with PVC is material, two of parallel placements band diamond-mesh the titanium electrode, filling 50ml press the catalyst A that embodiment 6 prepares, use the pump continuous sample introduction, under certain impressed current condition, adopt different air speeds, handle.Each water sample is got numerical value after the complete equipilibrium.
20 ℃ of temperature of reaction, normal pressure, former water COD
Cr: 380mg/L.Electric-multiphase catalytic reaction voltage: 10V, current density: the 100mA/ square decimeter, reaction back pH:7 the results are shown in table 5.
Table 5. is through the electric-multiphase catalytic result of pretreated cutting fluid waste water
| Air speed (V Water∶V Catalyzer) | 1.5 | 22 | 2.6 | 3.0 | 3.4 | 4.1 |
| Reaction back COD Cr(mg/L) | 62.3 | 79.1 | 83.4 | 88.7 | 94.5 | 112 |
| Clearance (%) | 83.61 | 79.18 | 78.05 | 76.66 | 75.13 | 70.53 |
Embodiment 7
Electric-multiphase catalytic for pretreated cutting fluid waste water is tested continuously
In reactor, the catalyst B of embodiment 6 preparations, 20 ℃ of temperature of reaction, normal pressure, former water COD are pressed in filling
Cr: 380mg/L.Electric-multiphase catalytic reaction voltage: 12V, current density: the 275mA/ square decimeter, reaction back pH:7, reaction result is listed in table 6.
Table 6. is through the electric-multiphase catalytic result of pretreated cutting fluid waste water
| Air speed (V Water∶V Catalyzer) | 1.5 | 2.2 | 2.6 | 3.0 | 3.4 | 4.1 |
| Reaction back COD Cr(mg/L) | 64.7 | 89.1 | 93.4 | 98.9 | 106.7 | 125 |
| Clearance (%) | 82.93 | 76.55 | 75.42 | 73.97 | 71.92 | 67.11 |
Embodiment 8
Electric-multiphase catalytic for pretreated cutting fluid waste water is tested III continuously
In reactor, and the catalyzer that filling prepares by embodiment 6 (weight of metal component is: Mn:3%), and 20 ℃ of temperature of reaction, normal pressure, former water COD
Cr: 380mg/L.Electric-multiphase catalytic reaction voltage: 15V, current density: the 400mA/ square decimeter, reaction back pH:7, reaction result is listed in table 6.
Table 6. is through the electric-multiphase catalytic result of pretreated cutting fluid waste water
| Air speed (V Water∶V Catalyzer) | 1.5 | 2.2 | 3.0 | 4.1 |
| Reaction back COD Cr(mg/L) | 61.5 | 80.7 | 92.4 | 106 |
| Clearance (%) | 83.82 | 78.76 | 75.68 | 72.11 |
Experimental result by embodiment is seen, uses flocculation-ultrafiltration reverse osmosis that cutting fluid waste water is handled, and reaches pretreated purpose, can remove most of organism, then carry out the electric-multiphase catalytic oxide treatment, can reach discharging standards, working cost is lower, and actual application value is arranged.
Claims (9)
1. the method for a coupling technique processing cutting liquid waste water, it is characterized in that: at first carry out air supporting-flocculation treatment: its pressure is 0.2～0.4Mpa, the consumption of flocculation agent is 0.1%～6% of a waste water weight; Carry out ultrafiltration-reverse-osmosis treated again: waste water is carried out the two-stage mocromembrane filter, its operating pressure is 0.05～0.6Mpa, carries out reverse osmosis then, and its operating pressure is 0.5～1.5Mpa; Carry out the electric-multiphase catalytic oxide treatment at last: its volts DS is 10～15V, current density is every square decimeter of 100mA-400mA, catalyzer is that the oxide compound with Fe or Mn is the loaded catalyst of active ingredient, and the content of its active ingredient is 1～4% of total catalyst weight, V
Waste water: V
Catalyzer=1.2～5.
2. by the method for the described coupling technique processing cutting of claim 1 liquid waste water, it is characterized in that: described flocculation agent is Tai-Ace S 150, ferrous sulfate, polymerize aluminum chloride or bodied ferric sulfate.
3. by the method for the described coupling technique processing cutting of claim 1 liquid waste water, it is characterized in that: in described air supporting-flocculation treatment, flocculation agent is polymerize aluminum chloride or bodied ferric sulfate, and its usage quantity is 0.1～2% of a waste water weight.
4. press the method for the described coupling technique processing cutting of claim 1 liquid waste water, it is characterized in that: add coagulant aids in described air supporting-flocculation treatment process, this coagulant aids is anionic polyacrylamide or cationic polyacrylamide, and its usage quantity is 0.001%～0.0025% of a waste water weight.
5. by the method for the described coupling technique processing cutting of claim 4 liquid waste water, it is characterized in that: described coagulant aids is an anionic polyacrylamide, and usage quantity is 0.0015% of a waste water weight.
6. press the method for the described coupling technique processing cutting of claim 1 liquid waste water, it is characterized in that: in the described ultrafiltration reverse-osmosis treated process, the filtering first step mocromembrane of two-stage mocromembrane aperture is 5 microns, and mocromembrane aperture, the second stage is 0.22 micron, and the anti-pressure ability of film is 0.3～0.6MPa; An exchange capacity of reverse-osmosis treated is for handling 15% of wastewater flow rate.
7. by the method for the described coupling technique processing cutting of claim 1 liquid waste water, it is characterized in that: described electric-multiphase catalytic oxide catalyst, the content of its active ingredient are 2～3% of total catalyst weight, its consumption V
Waste water: V
Catalyzer=2.6～3.0.
8. press the method for the described coupling technique processing cutting of claim 1 liquid waste water; it is characterized in that: described catalyzer can adopt immersion process for preparing: is in the soluble chloride or nitrate aqueous solution of the metal cations Fe of 0.12～1.0mol/L or Mn with carrier impregnation in concentration; leave standstill; oven dry; in 300～450 ℃, roasting got final product in 4～8 hours under nitrogen protection again.
9. by the method for the described coupling technique processing cutting of claim 8 liquid waste water, it is characterized in that: in the described Preparation of Catalyst, solution is 0.8～1.5: 1 with the carrier bulk ratio; Described leaving standstill is meant under 25～30 ℃ of conditions and put 10～24 hours; Bake out temperature is 110～130 ℃.
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| CN101723523B (en) * | 2008-10-24 | 2012-08-29 | 中国石油化工股份有限公司 | Treatment method for dry acrylic fiber production wastewater |
| CN101565214B (en) * | 2009-03-05 | 2011-08-10 | 杨火东 | Stone cutting wastewater treatment agent and wastewater treatment recovery method as well as device thereof |
| CN102211832B (en) * | 2010-04-01 | 2013-02-27 | 深圳市兰科环境技术有限公司 | Method for treating cutting fluid wastewater by photocatalytic oxidation |
| CN105347572A (en) * | 2015-12-02 | 2016-02-24 | 仲小勇 | Automobile wastewater circulating treatment system and automobile wastewater circulating treatment method |
| CN108081025A (en) * | 2016-11-23 | 2018-05-29 | 环驰云和钢球有限公司 | A kind of method that cutting fluid recycles |
| CN106977012A (en) * | 2017-04-21 | 2017-07-25 | 合肥市瀚坤机械有限公司 | A kind of used cutting liquid processing method |
| CN111533311B (en) * | 2020-05-11 | 2023-10-13 | 华辰环保能源(广州)有限责任公司 | Method for filtering and recovering valuable metals by chemically combining cutting fluid with membrane |
| CN112174441A (en) * | 2020-10-21 | 2021-01-05 | 南京江岛环境科技研究院有限公司 | System and method for treating and recycling machining wastewater by using air flotation pretreatment, biochemistry and double-membrane method |
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| US4555345A (en) * | 1981-01-22 | 1985-11-26 | Sankyo Yuki Kabushiki Kaisha | Method of treatment for separation of oil from oil-containing slurry waste |
| CN1266026A (en) * | 2000-04-03 | 2000-09-13 | 上海恒通水处理工程有限公司 | Water quality depth treatment process |
| CN1382650A (en) * | 2001-04-20 | 2002-12-04 | 上海金迪生物技术工程有限公司 | Process for comprehensively treating high-concentration water organic water |
| CN1410372A (en) * | 2002-10-16 | 2003-04-16 | 中国科学院大连化学物理研究所 | Method of treating oil field waste water using flocculation electro multiphase catalysis and special flocculation equipment |
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- 2004-07-16 CN CNB2004100209827A patent/CN1312048C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4555345A (en) * | 1981-01-22 | 1985-11-26 | Sankyo Yuki Kabushiki Kaisha | Method of treatment for separation of oil from oil-containing slurry waste |
| CN1266026A (en) * | 2000-04-03 | 2000-09-13 | 上海恒通水处理工程有限公司 | Water quality depth treatment process |
| CN1382650A (en) * | 2001-04-20 | 2002-12-04 | 上海金迪生物技术工程有限公司 | Process for comprehensively treating high-concentration water organic water |
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