CN1139541C - Process for equipment for deeply treating organic waste water - Google Patents
Process for equipment for deeply treating organic waste water Download PDFInfo
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- CN1139541C CN1139541C CNB011079894A CN01107989A CN1139541C CN 1139541 C CN1139541 C CN 1139541C CN B011079894 A CNB011079894 A CN B011079894A CN 01107989 A CN01107989 A CN 01107989A CN 1139541 C CN1139541 C CN 1139541C
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- waste water
- aluminate
- adsorption column
- silico
- active carbon
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Abstract
The present invention relates to a method for deeply treating organic waste water. The present invention carries out adsorption and purification treatment through an adsorption column which is filled with an active carbon filling material containing aluminium silicate with the general formula of Mx/n [(AlO2)*(SiO2)y] and is added with a direct-current field. The resistance value of the filling material column is from 50% to 75% lower than that of a common column, the current of the filling material column is from 0.1 to 1A, and the voltage is from 1 to 30V. The removing rate of CODcr is more than 50%, and is enhanced by more than 10% higher than that of the common active carbon column, and the service life is extended by more than one times. The present invention has the advantage of simple equipment, high efficiency of the purification treatment, strong purification, easy operation, investment saving, long operation cycle, low operating cost and wide application in water treating engineering.
Description
Technical field
The present invention relates to technical field of waste water processing, more specifically say so about a kind of treatment technology with electrochemical activity charcoal adsorption deeply purification of organic waste water.
Background technology
At present, waste water advanced process field gac commonly used is as sorbent material, with the pollutent that removes in the water, reach the purpose that purifies water, the defective that this method exists is: operation for some time, the charcoal absorption capacity reaches exhaustion print (breakthrough point) very soon, and gac need be changed or regenerate, its expense is very high and loaded down with trivial details, and this is the principal element that restriction adsorption cleaning treatment technology is promoted and developed.In fields such as dyeing waste waters, the research report that adopts the absorption of electrochemical activity charcoal is arranged, in the time of the charcoal absorption organic pollutant, under the effect of DC electric field, partial oxidation decomposes the organic pollutant that is adsorbed on activated carbon surface or inside, has improved the loading capacity of gac.But the specific conductivity of medium (gac and waste water) is lower, and normal the employing adds rare electrolyte solution, shortens two interpolar distance or sneak into the particulate state or the laminal filler that can improve specific conductivity in gac in the prior art, improves medium conductivity.Above method is feasible in the laboratory, and there are a lot of problems in engineering in using, as adds rare electrolyte solution, easily causes secondary pollution; Shorten negative electrode, positive interpolar distance, can reduce waste water treatment efficiency greatly; Sneak into the particulate state or the laminal filler that can improve specific conductivity, then because filler proportion is very difficult close with gac, easy layering during back flushing causes and mixes inequality, does not have the effect that improves specific conductivity.
Summary of the invention
The object of the present invention is to provide a kind of detergent power strong, long service life is easy to the electrochemistry adsorption technology of applying industrial.
We know that absorption can be divided into physical adsorption, chemisorption and ion-exchange absorption.Produce absorption with intermolecular gravitation and cry physical adsorption.To have produced chemical action between sorbent material and the adsorbate, the absorption that the generation chemical bond causes is called chemisorption.The absorption that is accompanied by equivalent ion-exchange between sorbent material and the adsorbate is adsorbed ion-exchange.In wastewater treatment, the synthesis result of physical adsorption often, chemisorption and ion-exchange absorption, the factor that influences adsorption effect is a lot, aspect intrinsic factor, the physicochemical property of sorbent material is arranged.As the specific surface area of sorbent material, hole structure, surface charging situation, intermolecular Van der Waals force etc., external cause have: wastewater property, turbidity, duration of contact etc.
Solution of the present invention is that a kind of general formula that contains of having packed in the adsorption column of said deep-treating organic waste water is M
X/n[(AlO
2)
x(SiO
2)
y] active carbon filler of silico-aluminate, and in adsorption column, be added with DC electric field.M is basic metal or alkaline earth metal cation in the said silico-aluminate general formula, and n represents the electric charge of metallic cation, and X/n represents the number of metallic cation, and said here silico-aluminate can be selected natural materials for use, also can synthetic.This sial salt can be scattered in separately among the filler, also can be combined into one with granulated active carbon.Preferred version of the present invention is that to have applied general formula be M to the pore surface at a gac
X/n[(AlO
2)
x(SiO
2)
y] sorbent material of the nanometer of silico-aluminate or the granulated active carbon of inferior nano coating.The content of this sial salt in granulated active carbon is 0.3-6.0wt%, and its preferred silico-aluminate content is 0.5-3.0wt%.And make the silico-aluminate of top coat, the content in granulated active carbon is 0.5-1.30wt%.The current value of DC electric field is 0.1-1A in adsorption column, and dc voltage value is 1-30V.
The adsorption column that constitutes like this, wherein silico-aluminate is a non-conducting material, gac belongs to electro-conductive material, we directly are compound in this silico-aluminate on the gac, utilize the composite conducting mechanism of the conductive characteristic and the charcoal monoxide of this nano material, this medium that is made of silico-aluminate one active carbon filler and waste water, its resistance value can reduce 50-75%.The physical strength of gac also increases simultaneously.Under External Electrical Field, the silico-aluminate of nanometer or inferior nano coating and activated carbon surface exist transfer transport and transmission, produce the binary interfacial effect, charged specific surface increases, form a lot of charged points, help adsorbing the pollutent that has electric charge, to micelle shape pollutent, can play and take off steady effect, thereby improve its adsorptive power.On nanometer or the sub-nano silica aluminate bigger surface-area is arranged, organism had very strong adsorptive power, also easy and activated carbon surface forms new interface, under effect of electric field, activate the active site (oxygen-containing functional group of gac chemisorption to a certain extent, as hydroxyl-OH, carbonyl=CO etc.), thus activated carbon adsorptive capacity improved.Moreover simultaneously at the charcoal absorption organic pollutant, under the effect of DC electric field, redox reaction takes place, can decompose the organic pollutant that is adsorbed on activated carbon surface or inside by partial oxidation, improve the loading capacity of gac, prolong the backwashing period of charcoal absorption.
In the present invention, organic waste water is by a kind of like this DC electric field that is added with, and be equipped with and carry out the deep chemical adsorption cleaning in the adsorption column of active carbon filler of silicon aluminate and handle, waste water residence time in adsorption column is 15-45 minute, its clearance can reach more than 50%.
For showing progressive of the present invention, we are with a kind of terylene waste water, done control experiment with common granulated active carbon adsorption column and the present invention, CODcr is 80-300mg/L after the trade effluent process biochemical treatment of production terylene and the filtration treatment, enter adsorption column and make adsorption treatment, compare the clearance of two kinds of methods under the same conditions, the results are shown in Table 1 CODcr.
Table 1 the present invention and common activated carbon column performance comparison
| Sequence number | Duration of service | Common gac | The present invention | The percentage point that clearance of the present invention improves | ||
| COD CrClearance (%) | Backwashing period (my god) | COD CrClearance (%) | Backwashing period (my god) | |||
| 1 | 1 month | 55.2 | 5 | 68.3 | 6 | 13.1 |
| 2 | 3 months | 50.1 | 3 | 65.5 | 5 | 15.4 |
| 3 | 6 months | 31.3 | 1 | 50.6 | 4 | 19.3 |
The clearance of CODcr of the present invention has improved more than 10 percentage points than common charcoal absorption as can be seen from Table 1, backwashing period prolongs 1-2 days, common gac clearance to CODcr after six months descends rapidly, backwashing period shortens to one day, the loading capacity of gac needs regeneration near exhaustion print.Clearance comparison of the present invention is high 19.3 percentage points according to post.
Description of drawings
The invention will be further described in conjunction with the accompanying drawings more below.
Accompanying drawing 1 is the synoptic diagram of the waste water advanced treatment unit of the present invention.
1 is packing layer in the accompanying drawing 1, and 2 is positive and negative electrode, and electrode is a parallel pole, and the electrode logarithm is one or more pairs of, selectes according to the actual needs that engineering is used; 3 is the tap water admission port, and 4 is air discharge ports; The 5th, back flushing air population, the 6th, backwash water outlet, the 7th, transforming valve.
Embodiment
After granulated active carbon floods in a kind of colloidal sol of silico-aluminate; taking-up is dried about 100 ℃, and carry out sintering processes under nitrogen protection after, activates with water vapor at last; make the active carbon filler of silicon aluminate of the present invention, in the adsorption column of packing into.
When carrying out purifying treatment, as shown in Figure 1, organic waste water after biochemical treatment and filtration, CODcr content is generally 80-300mg/L, enter adsorption column from the bottom, 0.2-0.6A galvanic current and 5-20V volts DS in addition, the residence time 15-45 of processed water in post minute, purifying waste water after the processing goes out from adsorption column top water outlet overflow, and this moment, the clearance of CODcr can reach 50-70%.
Adsorption column when the CODcr of adsorption column clearance descends 15% left and right sides than initial value, need carry out a back flushing after operation for some time.The main purpose of back flushing is to remove particulate pollutant that gac holds back and most of organism of physical adsorption.Back flushing is washed with tap water, said backwash operation as shown in the figure, at this moment, elder generation's conversion valve 7 stops waste water and enters, and tap water enters pillar from the top 3 of adsorption column, 6 flow out from adsorption column bottom, and the water (flow) direction of water (flow) direction during with purifying treatment is just in time opposite.Meanwhile, feed the pressurized air of 0.05MPa left and right sides pressure in adsorption column bottom 5, play stirring action, to improve backwash effect.Backwashing time, each about about 15 minutes.When the water outlet of back flushing becomes clear, the content of suspended solid is reduced to 2mg/L when following, and back flushing is finished, and can proceed to purify waste water to handle and operate.The backwashing period of adsorption column of the present invention is as shown in table 1, and when the CODcr of adsorption column after back flushing clearance still was lower than 30%, filler then needed regeneration in the post, and its renovation process can be undertaken by common regeneration of activated carbon method.If regeneration back adsorption column specific conductivity obviously descends then because silico-aluminate comes off seriously, need handle active carbon filler of the present invention again this moment by aforesaid preparation method.Compare with common gac, the present invention use through the modified active carbon filling material, can prolong more than one times its work-ing life.
In a word, advantage of the present invention is clearly, uses treatment unit of the present invention, has solved the low difficult problem of prior art medium specific conductivity, does not need to add dielectric medium, or additive method reduces its resistance value, makes the application of this electrochemical adsorption technology on engineering become practical.The used modified active carbon filling material of the present invention is compared with common gac, can prolong its work-ing life more than one times, and its CoDcr clearance improves more than 10 percentage points.With apparatus of the present invention processing of purifying waste water, detergent power is strong, and power consumption is low, and the treating water residence time is short, the processing efficiency height.Technology of the present invention, equipment is simple, and is easy and simple to handle, and investment and economic operating cost can be used in waste water advanced process field, also can be applicable to other and give water treatment field, and popularizing application prospect is widely arranged.
The invention will be further described to use several embodiment below again, is not confined to certainly among these several examples.
Embodiment 1
The content of silico-aluminate is 0.5-0.6wt%, surplusly is that granular active carbon forms adsorption unit.Waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, magnitude of voltage 15V, and retention time of sewage 20min moves more than 1 month continuously, and the CODcr clearance is 58.6%.
The content of silico-aluminate is 1-1.2wt%, surplusly is that granular active carbon forms adsorption unit, and waste water COD cr for the 80-150mg/L current value is, 0.3-0.5A, magnitude of voltage is 15V retention time of sewage 20min, moves continuously more than 1 month, and the CODcr clearance is 69.0%.Embodiment 3
The content of silico-aluminate is 1.8-2wt%, surplusly is that granular active carbon forms adsorption unit, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, magnitude of voltage 15V, and retention time of sewage 20min moves 2 months continuously, and the CODcr clearance is 58.3%.
Embodiment 4
To be that 1-1.2wt% is surplus be that granular active carbon forms adsorption unit to the content of silico-aluminate, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, and magnitude of voltage is 8V, and retention time of sewage 20min moves 4 months continuously, and the CODcr clearance is 63.2%.
To be that 1.8-2.0wt% is surplus be that granular active carbon forms adsorption unit to the content of silico-aluminate, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, and magnitude of voltage is 8V, and retention time of sewage 20min moves 6 months continuously, and the CODcr clearance is 52.3%.
Embodiment 6
To be that 3-3.3wt% is surplus be that granular active carbon forms adsorption unit to the content of silico-aluminate, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, and magnitude of voltage is 20V, and retention time of sewage 20min moves 2 months continuously, and the CODcr clearance is 59.6%.
Embodiment 7
To be that 3.5-3.8wt% is surplus be that granular active carbon forms adsorption unit to the content of silico-aluminate, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, magnitude of voltage is 25V, retention time of sewage 20min moves 2 months continuously, and the CODcr clearance is 55.6%.
Embodiment 8
To be that 5-5.5wt% is surplus be that granular active carbon forms adsorption unit to the content of silico-aluminate, and waste water COD cr is 80-150mg/L, and current value is 0.3-0.5A, and magnitude of voltage is 25V, and retention time of sewage 20min moves 2 months continuously, and the CODcr clearance is 56.7%.
Claims (7)
1, a kind of method of deep-treating organic waste water is characterized in that waste water is to be added with DC electric field and to be equipped with that to contain general formula be M by a kind of
X/n[(AlO
2)
x(SiO
2)
y] adsorption column of active carbon filler of silico-aluminate carries out the electrochemistry adsorption cleaning and handle.
2, according to the described deep treatment method of claim 1, the current value that it is characterized in that being added in the DC electric field in the adsorption column is 0.1-1A, and dc voltage value is 1-30V.
3,, it is characterized in that the residence time of waste water in adsorption column is 15-45 minute according to the described deep treatment method of claim 1.
4,, it is characterized in that being equipped with in the adsorption column that to contain general formula be M according to the described device that is used for deep-treating organic waste water of claim 1
X/n[(AlO
2)
x(SiO
2)
y] active carbon filler of silico-aluminate, and in adsorption column, be added with DC electric field.
5,, it is characterized in that said filler is that to scribble one deck general formula at the granulated active carbon pore surface be M according to the device of the described deep-treating organic waste water of claim 4
X/n[(AlO
2)
x(SiO
2)
y] nanometer of silico-aluminate or the granule adsorbent of inferior nano coating.
6, according to the device of the described deep-treating organic waste water of claim 5, the content that it is characterized in that the silico-aluminate of particles used sorbent material in the adsorption column is 0.3-6.0wt%.
7, according to the device of the described deep-treating organic waste water of claim 6, the content that it is characterized in that the silico-aluminate of particles used sorbent material in the adsorption column is 0.5-3.0wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079894A CN1139541C (en) | 2001-04-16 | 2001-04-16 | Process for equipment for deeply treating organic waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079894A CN1139541C (en) | 2001-04-16 | 2001-04-16 | Process for equipment for deeply treating organic waste water |
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| CN1381404A CN1381404A (en) | 2002-11-27 |
| CN1139541C true CN1139541C (en) | 2004-02-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863084A (en) * | 2012-09-07 | 2013-01-09 | 常州大学 | Method for degrading organic wastewater through electrolytic stimulation of mineralized refuse supported microorganisms |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ534551A (en) | 2004-08-06 | 2006-01-27 | Water Rite Ltd | Water treament apparatus with bacterial culture medium |
| CN103122255B (en) * | 2006-01-30 | 2016-01-20 | 诚实公司 | For fluid storage/distribution carbonaceous material and utilize its apparatus and method |
| US8679231B2 (en) | 2011-01-19 | 2014-03-25 | Advanced Technology Materials, Inc. | PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
| CN105110405B (en) * | 2015-08-14 | 2018-10-12 | 中国石油化工股份有限公司 | Electricity enhancing activated carbon adsorption wastewater treatment method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863084A (en) * | 2012-09-07 | 2013-01-09 | 常州大学 | Method for degrading organic wastewater through electrolytic stimulation of mineralized refuse supported microorganisms |
| CN102863084B (en) * | 2012-09-07 | 2014-01-08 | 常州大学 | Method for degrading organic wastewater through electrolytic stimulation of mineralized refuse supported microorganisms |
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|---|---|
| CN1381404A (en) | 2002-11-27 |
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