CN102745772A - Microwave assisted organic bentonite synthesis-oily wastewater treatment integrated process - Google Patents
Microwave assisted organic bentonite synthesis-oily wastewater treatment integrated process Download PDFInfo
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- CN102745772A CN102745772A CN2012102731498A CN201210273149A CN102745772A CN 102745772 A CN102745772 A CN 102745772A CN 2012102731498 A CN2012102731498 A CN 2012102731498A CN 201210273149 A CN201210273149 A CN 201210273149A CN 102745772 A CN102745772 A CN 102745772A
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Abstract
The invention relates to a microwave assisted organic bentonite synthesis-oily wastewater treatment integrated process. The process includes adding the untreated bentonite with particle sizes of 10-200 meshes and a cationic surface active agent into the oily wastewater, adding the wastewater into an ultrasonic wave reactor, applying ultrasonic waves with frequency of 20KHz-120KHz and power of 100W-1200W for 10 seconds to 5 minutes for purifying treatment, simultaneously, stirring the wastewater, then stirring the wastewater for 2-3 minutes after the ultrasonic treatment is finished and then performing solid/liquid two-phase separation, wherein the usage amount of the cationic surface active agent is 20%-120% of cation-exchange capacity (CEC), and the solid/liquid mass ratio of the bentonite to the oily wastewater is (1:1000)-(1:10000). The microwave assisted integrated process is capable of simply and effectively treating the oily wastewater.
Description
Technical field
The present invention relates to a kind of ultrasonic synergistic organobentonite synthesizes-handle the oily(waste)water integral process, belong to technical field of sewage in the environment protection.
Background technology
Oily(waste)water is a kind of waste water that has a large capacity and a wide range, has hazardness.It is mainly derived from oil production processing, petrochemical complex, metallurgy, mechanical industry, weaving, food-processing industry and sea transport industry etc.Its staple comprises: hydrocarbon polymer, fuel oil, tar, lubricating oil, wax, cerolein, soap class etc.
Oil in waste water mainly contains following several kinds:
(1) oil slick: the common major part of oil content that gets into water body exists with the oil slick form, and oil bead diameter is bigger, generally greater than 100 μ m, can comparatively fast float after leaving standstill, and keeps afloat with the oil film of external phase.Owing to have certain density difference between water and the oil, adopt gravitational separation process and transverse flow oil eliminator usually for oil slick.
(2) dispersed oil: particle diameter be the small oil droplet suspended dispersed of 10-100 μ m at aqueous phase, dispersed oil is unstable, leaves standstill if any time enough, can be gathered into bigger oil droplet and on float to the water surface.Such oil can adopt air supporting method and absorption method to remove.The most frequently used sorbing material is a gac, and it has good oil absorptiveness, the dispersed oil in the adsorbable waste water, oil in water emulsion and dissolving oil.But loading capacity limited (oil is generally 30-80mg/g), and the gac price is more expensive, and regeneration is also relatively more difficult, and is therefore general only as processing of lower concentration oily(waste)water or advanced treatment.
(3) oil in water emulsion: particle diameter is that the oil droplet of 0.1-10 μ m stably is scattered in the water, because oil droplet is atomic little, is between the 0.1-2 μ m mostly, therefore is difficult to make oily water separation with settled process merely.The particle diameter of oil in water emulsion is extremely small, in water, forms water-oil emulsion, and the surface forms one deck limitans and has electric charge, and the peripheral electrostatic double layer that forms of oil droplet makes the mutual repeller of oil droplet inaccessibility.Therefore, make oily water separation, at first will destroy the limitans of oil droplet, make oil droplet each other near and be gathered into big oil dripping pearl, thereby bubble through the water column, this process is breakdown of emulsion.Usually the sewage behind the breakdown of emulsion need utilize the method that oil slick is removed and dispersed oil is removed that it is carried out subsequent disposal again.
(4) dissolving oil: be scattered in the water body with molecularity, the elaioleucite diameter is also littler than emulsion, reaches several nanometers sometimes, and oil content and water form the homogeneous phase system, and is highly stable, is difficult to remove with general method.The membrane filter method oil removing is to utilize microporous membrane interception elaioleucite, and it is mainly used in removes oil in water emulsion and dissolving oil.The membrane filter method technical process is simple, and treatment effect is good, and water outlet does not generally have oil, but facility investment is huge, and treatment capacity is less, not too is suitable for extensive wastewater treatment, and the strainer easy blocking.
Wilkinite is to be the tonstein of essential mineral with smectite (Montmorillonite).Smectite is a kind of aqueous layer aluminosilicate mineral, forms by aluminium of two silicon-oxy tetrahedron therebetween (magnesium) oxygen (hydrogen-oxygen) are octahedra, belongs to the three-layer clay mineral of 2:1 type.Lattice spacing is from being 0.96 ~ 2.14nm, and these nanometer lamellas are reunited together, forms the clay particle that the hundreds of nanometer arrives several microns.Since the wetting ability that wilkinite surface silicon oxide structure is extremely strong and the hydrolysis of interlayer cation, the non-constant of performance of the wilkinite adsorption treatment organic pollutant of non-modified.But wilkinite has very strong CEC, under certain physical-electrochemical conditions, and Ca not only
2+, Mg
2+, Na
+, K
+Deng can exchanging each other, and can and organic cation (like cats product) exchange crystal layer between positively charged ion.Cationic exchange property is bentonitic important process characteristic, utilizes this characteristic, can carry out modification to wilkinite, like the preparation organobentonite.
Quaternary cationics is a preparation organobentonite organic cation commonly used, gets into bentonitic interlayer through ion exchange, makes the organobentonite that oily(waste)water is had better processing power, particularly to dissolving oil.(referring to metal mine, 2010 the 3rd phases, 154 pages; 228 pages of chemical industry journal 2008 the 1st phases).But this treatment agent is complex process, loaded down with trivial details in the process of preparation, comprises bentonite in powder is scattered in slurrying in the organically-modified agent solution, retrofits, and washs then, filters, dries, pulverizes, and obtains the organobentonite product.This method needs water bath with thermostatic control, stirs more than 2 hours when slurrying; Time consumption and energy consumption and consume water resources; And have to produce the waste water that contains the exhibiting high surface promoting agent, need further to handle, bentonite synthesis technique stability is bad in addition; Directly influenced bentonite modified quality, these have all limited the application of organobentonite in wastewater treatment and contaminate environment reparation.
Summary of the invention
The technical problem that the present invention will solve is: overcome complex process in the prior art, the big deficiency that consumes energy provides a kind of ultrasonic synergistic organobentonite to synthesize-processing oily(waste)water integral process, and this method can be handled oily(waste)water simply and effectively.
For solving the problems of the technologies described above the technical scheme that the present invention adopts being: a kind of ultrasonic synergistic organobentonite is synthetic-handle the oily(waste)water integral process; With particle diameter is that undressed wilkinite of 10 ~ 200 orders and cats product join in the oily(waste)water; The cats product consumption is 20% ~ 120%CEC; The dosage of cats product calculates according to cation exchange capacity; 20%CEC representes that the 20% positively charged ion capacity that exchanges needs the amount of cats product, is 80mmol/g such as certain bentonitic cation exchange capacity, and the exchange capacity of 20%CEC is to need to add the 16mmol cats product in every gram wilkinite.The solid-liquid mass ratio of wilkinite and oily(waste)water is 1:1000 ~ 1:10000, then this waste water is added in the ultrasound reactor, and applying frequency is 20kHz ~ 120KHz; Power is the UW of 100W ~ 1200W; Ultrasonication 10s ~ 5min carries out purifying treatment, stirs simultaneously, and supersound process finishes back restir 2-3min; Carry out solid-liquid two again and be separated, waste water is purified handles the back discharging.
The used wilkinite of the present invention is to mill after the exploitation to obtain particle and need not to pulverize than coarse particles, can utilize the ultra-sonic dispersion function, according to the particle size proper extension sonic oscillation time, can reach higher removal efficient.Wilkinite after the processing and waste water mixture can take spinning or filter type to reach the solid/liquid separation purpose.
The ultrasound reactor that the present invention uses is formed as ultrasonic generator, shake case and reaction chamber.Handle in the reaction chamber and be generally batch operation, can be used for the wastewater treatment occasion that hydraulic load is little, emission standard is higher, oleaginousness is higher, can reach direct emission request through regulating the operating procedure condition; Add transmission medium (being generally water) in the reaction chamber; The waste water coil pipe is set in the reaction chamber; Coil pipe is immersed in the transmission medium, and waste water is accepted ultra-sonic oscillation through transmission medium and can be used for continous way or semi continuous operation in pipeline, be applicable to that wastewater flow rate is big, the quantity-produced occasion; Can handle the not too high waste water of oleaginousness, look the wastewater characteristics difference and can take different process such as directly discharging or entering next stage treatment unit.Reactor drum pattern of the present invention is not limited to these two types.
The contained oil pollutant of above-mentioned oily(waste)water comprise oil, crude oil, moving and plant, thing grease etc.But the present invention is suitable for the oil pollutant of handling and is not limited to these kinds.
Consider the requirement of organic pollutant content and emission standard in the pending waste water, can reach different treatment effects through changing bentonitic consumption.Bentonitic consumption is measurement index with wilkinite with pending wastewater quality ratio.Generally, take all factors into consideration and handle effect and process economy, wilkinite and pending wastewater quality can be between 1:1000 ~ 1:10000 than scope, but the present invention is not limited to this level.
Used cats product is the long chain type cats product, and the alkyl carbon atoms number is more than 8.
The invention has the beneficial effects as follows:
(1) shortened operation steps, avoided the loaded down with trivial details process of synthetic organobentonite, bentonite has been synthesized with wastewater treatment in same process, accomplish, used wilkinite and tensio-active agent are more economized than technology in the past in this process; Bentonitic particle can be thicker, under action of ultrasonic waves, can disperse rapidly.
(2) UW helps the oil in water emulsion breakdown of emulsion, promotes oily water separation.
(3) the oily(waste)water purifying treatment time shortens, and efficient improves.The drum oscillation treatment of utilizing the ultrasonic cavitation effect to produce; The wilkinite original soil is accomplished rapidly and cats product exchange modification and adsorbed oil pollutant process; Realize that the difficult degradation oily(waste)water obtains efficient adsorption cleaning at short notice, reaches emission standard.
Embodiment
Through embodiment the present invention is done further explain below.
Embodiment 1
With particle diameter is that the cats product chloro-hexadecane yl pyridines of undressed wilkinite of 10 orders and 20%CEC joins and contains in the edible oil waste water, and wilkinite and waste water solid-liquid mass ratio are 1:1000, then this waste water of 1L are inserted in the ultrasound reactor; Applying frequency is 20kHz; The UW of power 100W, ultrasonication 5min carries out purifying treatment, stirs simultaneously; Supersound process finishes back restir 2min; Adopt the spinning mode to carry out solid-liquid two again and be separated, through measuring, the clearance of oil is greater than 99% in the waste water.
The organobentonite that the cats product modification of same amount and identical type obtains is not having under the UW effect, and the adsorption through the identical time only has 30.1% to the oils clearance in the identical waste water.
Embodiment 2
With particle diameter is that the cats product cetyl trimethylammonium bromide of undressed wilkinite of 200 orders and 120%CEC joins and contains in the crude oil waste water, and wilkinite and waste water solid-liquid mass ratio are 1:10000, then this waste water of 1L are inserted in the ultrasound reactor; Applying frequency is 120KHz; The UW of power 1200W, ultrasonication 5min carries out purifying treatment, stirs simultaneously; Supersound process finishes back restir 3min; Adopt filter type to carry out solid-liquid two again and be separated, through measuring, the clearance of oil is greater than 96% in the waste water.
The organobentonite that the cats product modification of same amount and identical type obtains is not having under the UW effect, and the adsorption through the identical time only has 49.1% to the oils clearance in the identical waste water.
Embodiment 3
With particle diameter is that cats product chloro eight alkyl pyridines of undressed wilkinite of 200 orders and 80%CEC join and contain in the diesel oil waste water, and wilkinite and waste water solid-liquid mass ratio are 1:1000, then this waste water of 1L are inserted in the ultrasound reactor; Applying frequency is 120KHz; The UW of power 1200W, ultrasonication 10s carries out purifying treatment, stirs simultaneously; Supersound process finishes back restir 3min; Adopt filter type to carry out solid-liquid two again and be separated, through measuring, the clearance of oil is greater than 99% in the waste water.
The organobentonite that the cats product modification of same amount and identical type obtains is not having under the UW effect, and the adsorption through the identical time only has 35.6% to the oils clearance in the identical waste water.
Embodiment 4
With particle diameter is that cats product chloro eight alkyl trimethyl ammonium bromides of undressed wilkinite of 10 orders and 60%CEC join and contain in the diesel oil waste water, and wilkinite and waste water solid-liquid mass ratio are 1:1000, then this waste water of 1L are inserted in the ultrasound reactor; Applying frequency is 120KHz; The UW of power 1200W, ultrasonication 3min carries out purifying treatment, stirs simultaneously; Supersound process finishes back restir 3min; Adopt the spinning mode to carry out solid-liquid two again and be separated, through measuring, the clearance of oil is greater than 99% in the waste water.
The organobentonite that the cats product modification of same amount and identical type obtains is not having under the UW effect, and the adsorption through the identical time only has 38.9% to the oils clearance in the identical waste water.
Embodiment 5
With particle diameter is that cats product chloro eight alkyl trimethyl ammonium bromides of undressed wilkinite of 10 orders and 60%CEC join by solid-to-liquid ratio 1:1000 and contain in the diesel oil waste water; Waste water is flowed through and is immersed in the coil pipe in the water in the ultrasonic response chamber; Ultrasonic frequency is 40kHz, and power is 1000W, and the residence time of waste water in coil pipe is 5min; Handle continuously after precipitate and separate, the clearance of measuring oil in the waste water is 98%.This process proof present method is fit to the continous way manipulation of oily(waste)water equally.
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and through above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification sheets, must confirm its technical scope according to the claim scope.
Claims (5)
1. a ultrasonic synergistic organobentonite synthesizes-handles the oily(waste)water integral process; It is characterized in that: with particle diameter is that undressed wilkinite of 10 ~ 200 orders and cats product join in the oily(waste)water, and the cats product consumption is 20% ~ 120%CEC, and the solid-liquid mass ratio of wilkinite and oily(waste)water is 1:1000 ~ 1:10000; Then this waste water is joined in the ultrasound reactor; Applying frequency is 20kHz ~ 120KHz, and power is the UW of 100W ~ 1200W, and ultrasonication 10s ~ 5min carries out purifying treatment; Stir simultaneously; Supersound process finishes back restir 2-3min, carries out solid-liquid two again and is separated, and waste water is purified handles the back discharging.
2. ultrasonic synergistic organobentonite according to claim 1 synthesizes-processing oily(waste)water integral process, and it is characterized in that: described solid-liquid two is separated and takes spinning or filter type.
3. ultrasonic synergistic organobentonite according to claim 1 synthesizes-processing oily(waste)water integral process, it is characterized in that: intermittent type, continous way or semi continuous operation are adopted in described ultrasonication.
4. ultrasonic synergistic organobentonite according to claim 1 synthesizes-processing oily(waste)water integral process, and it is characterized in that: the contained oil pollutant of described oily(waste)water comprises oil, crude oil and animal and plant grease.
5. ultrasonic synergistic organobentonite according to claim 1 synthesizes-processing oily(waste)water integral process, and it is characterized in that: described cats product is the long chain type cats product, and the alkyl carbon atoms number is more than 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150661A (en) * | 2014-08-22 | 2014-11-19 | 山西潞安矿业(集团)有限责任公司 | Method and device for separation of gas water tar |
| CN107726329A (en) * | 2017-10-08 | 2018-02-23 | 梁金秀 | Magnetic tape trailer heat utilization and the sinusoidal pulley type waste water processing unit of roots blower |
| CN107860006A (en) * | 2017-10-08 | 2018-03-30 | 吉首大学 | Sinusoidal pulley type municipal wastewater refuse disposal installation with dragveyer |
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| CN1462726A (en) * | 2003-04-07 | 2003-12-24 | 浙江大学 | Integral method of synthesizing organobentonite-treating wastewater |
| CN201031191Y (en) * | 2007-04-12 | 2008-03-05 | 江苏金山环保工程有限公司 | High concentration emulsifying waste water demulsifying device |
| CN101134609A (en) * | 2007-08-07 | 2008-03-05 | 江苏工业学院 | Method for processing organic wastewater by employing ultrasonic wave and synergic organophilic bentonite |
| US20120145633A1 (en) * | 2010-12-09 | 2012-06-14 | General Electric Company | Ultra-sound enhanced centrifugal separation of oil from oily solids in water and wastewater |
-
2012
- 2012-08-02 CN CN2012102731498A patent/CN102745772A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462726A (en) * | 2003-04-07 | 2003-12-24 | 浙江大学 | Integral method of synthesizing organobentonite-treating wastewater |
| CN201031191Y (en) * | 2007-04-12 | 2008-03-05 | 江苏金山环保工程有限公司 | High concentration emulsifying waste water demulsifying device |
| CN101134609A (en) * | 2007-08-07 | 2008-03-05 | 江苏工业学院 | Method for processing organic wastewater by employing ultrasonic wave and synergic organophilic bentonite |
| US20120145633A1 (en) * | 2010-12-09 | 2012-06-14 | General Electric Company | Ultra-sound enhanced centrifugal separation of oil from oily solids in water and wastewater |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150661A (en) * | 2014-08-22 | 2014-11-19 | 山西潞安矿业(集团)有限责任公司 | Method and device for separation of gas water tar |
| CN107726329A (en) * | 2017-10-08 | 2018-02-23 | 梁金秀 | Magnetic tape trailer heat utilization and the sinusoidal pulley type waste water processing unit of roots blower |
| CN107860006A (en) * | 2017-10-08 | 2018-03-30 | 吉首大学 | Sinusoidal pulley type municipal wastewater refuse disposal installation with dragveyer |
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Application publication date: 20121024 |