CN103420454A - Method for removing organic phosphorus of sewerage of circulating cooling water system - Google Patents
Method for removing organic phosphorus of sewerage of circulating cooling water system Download PDFInfo
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- CN103420454A CN103420454A CN2013103352582A CN201310335258A CN103420454A CN 103420454 A CN103420454 A CN 103420454A CN 2013103352582 A CN2013103352582 A CN 2013103352582A CN 201310335258 A CN201310335258 A CN 201310335258A CN 103420454 A CN103420454 A CN 103420454A
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- cooling water
- waste
- recirculated cooling
- organic phosphine
- waste iron
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Abstract
The invention relates to a method for removing organic phosphorus of sewerage of a circulating cooling water system, which comprises the following steps: acquiring and cleaning waste scrap irons, using acid to activate the waste scrap irons, water washing to neutral, weighing processed waste scrap irons, and adding active carbon granules, wherein the mass ratio of the active carbon to the waste scrap irons is 1:(1-5), mixing uniformly, pouring the corrosion and scale inhibitor of phosphorus system contained sewerage of the circulating cooling water system into a reactor with the waste scrap irons and the active carbon, and conducting solid-liquid separation after stirring reaction so as to remove phosphorus in the waste water, wherein the pH is close to neutral. According to the method, the waste scrap irons and the active carbon granules are utilized to generate substances with high-activity through microelectrolysis, so that organic phosphorus is transformed into inorganic phosphorus easy to be removed; Fe<2+> generated by electrolysis can be oxidized into Fe<3+> which can remove most inorganic phosphorus and organic phosphorus through manner of flocculation and coprecipitation. The method uses the waste scrap irons as a processing raw material, so that the cost is low, the recycle of waste is realized, and the practical significance of 'treating waste with waste' is adopted.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of method of removing organic phosphine, particularly a kind of recirculated cooling water sewer is removed the method for organic phosphine.
Background technology
Phosphine is that corrosion inhibiting and descaling agent is that maximum water treatment agents is applied in the industrial circulating cooling water aspect, phosphorus in recirculated cooling water exists with the form of organic, cause thus in recirculated cooling water containing certain density organic phosphine, the concentration of phosphine in recirculated cooling water at 2.5mg/L(in total phosphorus) left and right.The quantity discharged of recirculated cooling water is very large, if directly be discharged into the Eutrophication Status that will cause or aggravate receiving water body in environment.Traditional waste water dephosphorization technology comprises biological degradation method, chemical precipitation method and absorption method etc.For recirculated cooling water, wherein except the biocide containing also containing suitable content corrosion inhibiting and descaling agent, and the biodegradability of organic phosphine is lower, therefore directly utilizes biological process cycle for the treatment of cooling water drainage sewage to be difficult to realize the purpose of qualified discharge.Due to the scale inhibition characteristic of organic phosphine, the chemical precipitation method that aluminium salt, molysite, calcium salt and magnesium salts be precipitation agent of take be difficult to equally with recirculated cooling water in the organic phosphine form, exist form precipitation containing phosphor contaminant and remove.Due to the loading capacity that is limited to sorbent material, selectivity and a regeneration difficult problem thereof, for the water yield, for huge recirculated cooling water, absorption method also is difficult to the phosphor-removing effect that reaches desirable.Therefore, seek suitable dephosphorization technique and solve in the recirculated cooling water sewer with regard to becoming that to take phosphine be the key of the corrosion inhibiting and descaling agent phosphorous pollutant emission problem that is Main Morphology.
Summary of the invention
For the defect existed in above-mentioned prior art, technical problem to be solved by this invention has been to provide a kind of method of removing organic phosphine in the recirculated cooling water sewer, has solved the organic phosphorus in the recirculated cooling water sewer in the prior art and has been difficult to the technical problem of effectively removing.
The invention provides a kind of recirculated cooling water sewer and remove the method for organic phosphine, comprise the steps:
The first step: a step of obtaining waste iron filing, the median size of described waste iron filing is between 1 ~ 3mm;
Second step: waste iron filing is soaked with strong base solution, then wash with water and remove surperficial greasy dirt, be washed till the neutral rear hydrochloric acid or the sulfuric acid activation that are 4 ~ 8% with mass percent concentration, the time of activation is 0.2 hour ~ 2 hours, then water rinses to neutral rear standby;
The 3rd step: measuring processed waste iron filing, be placed in reactor, is 1:(1 ~ 5 according to the mass ratio of gac and waste iron filing) ratio mix activated carbon granule, mix;
The 4th step: will pass into containing the discharged circulated cooling water of organic phosphine the reactor of waste iron filing and gac, stirring reaction;
The 5th step: react after 0.5 ~ 3 hour and carry out solid-liquid separation, measure total phosphorus concentration and wastewater pH.
Further, described organic phosphine is as the phosphine based compound of corrosion inhibiting and descaling agent in recirculated cooling water.
Further, described gac median size is between 2 ~ 6mm.
Further, described strong base solution is sodium hydroxide solution or potassium hydroxide or the aqua calcis that mass percent concentration is 4 ~ 6%.
Further, the temperature of described strong base solution is between 40 ~ 70 ℃.
Concrete, it is in order to remove surface film oxide that the present invention adopts strong acid to soak waste iron filing, increases the iron filings roughness simultaneously, to increase the iron filings surface-area, and the activation waste iron filing.
Iron-carbon micro-electrolysis technique is based on the result of the comprehensive actions such as redox, absorption, flocculation to the removal of pollutent.At first waste iron filing is a kind of porous material, can adsorb the phosphine in waste water by physisorption; Secondly, the iron carbon mixture can form numerous micro-galvanic cell in electrolyte solution, this slightly galvanic cell take iron as anode, carbon be negative electrode generation redox reaction, concrete reaction equation is as follows:
Anode Fe → Fe
2++ 2e (1)
Negative electrode 2H
++ 2e → 2[H] → H
2(2)
O
2+ 4H
++ 4e → 2H
2O (acidic conditions) (3)
O
2+ 2H
2O+4e → 4OH
-(neutrality or alkaline condition) (4)
The high reactivity material generated can be corrosion inhibiting and descaling agent generation redox reaction with phosphine, and the organic phosphine is oxidized to and is easy to the Inorganic phosphorus of removing; The Fe constantly generated
2+Be oxidized to Fe when aerobic
3+, the high-polymerization degree Fe (OH) with flocculation activity generated under alkaline condition
3Colloid, can remove the organic phosphine suspended colloidal material in water with forms such as flocculation absorption, co-precipitation; In addition, Fe
2+Or Fe
3+Can also directly with the inorganic phosphate radical generated, form the tertiary iron phosphate precipitation.
The present invention compares with prior art, and its technical progress is significant.The present invention utilizes waste iron filing and activated carbon granule, by micro-electrolytic action, produces the high reactivity material (as nascent state [H] and Fe
2+(acidic conditions) or [OH] and Fe
2+(neutrality or alkaline condition)), the organic phosphine in recirculated cooling water is converted into and is easy to the Inorganic phosphorus of removing; The Fe that electrolysis produces
2+Can be oxidized to Fe
3+, form Fe (OH) under alkaline environment
2Or Fe (OH)
3Colloid, can by the flocculation mode remove a part of Inorganic phosphorus or organic phosphine, in addition, the inorganic phosphate radical of generation can with Fe
2+, Fe
3+Form calcium phosphate precipitation and removed.Present method application waste iron filing is for processing raw material, with low cost, has realized the recycling of refuse, has the realistic meaning of " treatment of wastes with processes of wastes against one another ".
Embodiment
Utilizing method of the present invention to process containing phosphine is power plant's circulating cooling system waste water of corrosion inhibiting and descaling agent.Before processing, the water-quality determination result is total phosphorus 2.45mg/L, and pH 8.76.Testing gac median size used is 2 ~ 3mm,
Operation steps is as follows:
The first step: a step of obtaining waste iron filing, the median size of described waste iron filing is between 1 ~ 3mm, and described waste iron filing is cast iron filing;
Second step: by 5% hot sodium hydroxide solution washing by soaking wipe oil for waste iron filing, be washed till neutral after with 5% hydrochloric acid activation 30min, rinse to neutral rear standby;
The 3rd step: measure the processed waste iron filing of 27g step (two) (calculating with not moisture waste iron filing), by the carbon weight of iron, than for 1:2.45, mixing activated carbon granule, mix and be placed in reactor, the gac median size of employing is 2 ~ 3mm;
The 4th step: the recirculated cooling water that is corrosion inhibiting and descaling agent containing phosphine by 250 mL passes into the reactor of iron carbon mixture, uses agitator with the 50r/min stirring and evenly mixing;
The 5th step: after reaction 1h, carry out solid-liquid separation and measure total phosphorus concentration and wastewater pH.
The total phosphorus concentration of measuring is 0.66mg/L, reaches " integrated wastewater discharge standard " (GB 8978-1996) secondary standard, to total tp removal rate, is that 72.95%, pH value is 6.97, and visible iron-carbon micro-electrolysis technology also has good regulating effect to waste water ph.
Claims (5)
1. the method for a recirculated cooling water sewer removal organic phosphine, is characterized in that comprising the steps:
The first step: a step of obtaining waste iron filing, described waste iron filing median size is between 1 ~ 3mm;
Second step: waste iron filing is soaked with strong base solution, then wash with water and remove surperficial greasy dirt, be washed till the neutral rear hydrochloric acid or the sulfuric acid activation that are 4 ~ 8% with mass percent concentration, soak time is 0.2 ~ 2 hour, then water rinses to neutral rear standby;
The 3rd step: measuring processed waste iron filing, be placed in reactor, is 1:(1 ~ 5 according to the mass ratio of gac and waste iron filing) ratio mix activated carbon granule, mix;
The 4th step: will pass into containing the recirculated cooling water sewer of organic phosphine the reactor of waste iron filing and gac, and stir;
The 5th step: react after 0.5 ~ 3 hour and carry out solid-liquid separation, measure total phosphorus concentration and wastewater pH.
2. a kind of recirculated cooling water sewer as claimed in claim 1 is removed the method for organic phosphine, it is characterized in that: described organic phosphine is as the phosphine based compound of corrosion inhibiting and descaling agent in recirculated cooling water.
3. a kind of recirculated cooling water sewer as claimed in claim 1 is removed the method for organic phosphine, and it is characterized in that: the median size of described gac is between 2 ~ 6mm.
4. a kind of recirculated cooling water sewer as claimed in claim 1 is removed the method for organic phosphine, and it is characterized in that: described strong base solution is the sodium hydroxide solution that mass percent concentration is 4 ~ 6%, or potassium hydroxide, or aqua calcis.
5. a kind of recirculated cooling water sewer as claimed in claim 1 is removed the method for organic phosphine, and it is characterized in that: described strong base solution temperature is between 40 ~ 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103352582A CN103420454A (en) | 2013-08-05 | 2013-08-05 | Method for removing organic phosphorus of sewerage of circulating cooling water system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103352582A CN103420454A (en) | 2013-08-05 | 2013-08-05 | Method for removing organic phosphorus of sewerage of circulating cooling water system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103420454A true CN103420454A (en) | 2013-12-04 |
Family
ID=49645896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103352582A Pending CN103420454A (en) | 2013-08-05 | 2013-08-05 | Method for removing organic phosphorus of sewerage of circulating cooling water system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496077A (en) * | 2014-12-22 | 2015-04-08 | 同济大学 | Deep scrap iron catalytic ozonation wastewater treatment method |
| CN104920465A (en) * | 2015-06-23 | 2015-09-23 | 上海金布梯环保科技发展有限公司 | Algae growth inhibiting composition and preparation method and application thereof |
| CN112811681A (en) * | 2019-11-15 | 2021-05-18 | 南京理工大学 | Zero-phosphorus discharge treatment process for circulating water phosphine system corrosion and scale inhibitor |
| CN115818850A (en) * | 2022-12-20 | 2023-03-21 | 浙江百斯特化工有限公司 | Composite phosphorus-free corrosion and scale inhibitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10225692A (en) * | 1996-12-11 | 1998-08-25 | Sanyo Electric Co Ltd | Treatment of waste water containing phosphoric acid ion and treatment device |
| CN1792843A (en) * | 2005-11-22 | 2006-06-28 | 南京工业大学 | Process of micro electrolysis pretreating PTA waste water |
| CN102050508A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Sewage treatment method for circulating cooling water system |
| CN102976532A (en) * | 2012-12-28 | 2013-03-20 | 湘潭大学 | Method for treating fluorine-containing polymetallic acidic smelting wastewater by internal electrolysis and coprecipitation of ferric-carbon |
-
2013
- 2013-08-05 CN CN2013103352582A patent/CN103420454A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10225692A (en) * | 1996-12-11 | 1998-08-25 | Sanyo Electric Co Ltd | Treatment of waste water containing phosphoric acid ion and treatment device |
| CN1792843A (en) * | 2005-11-22 | 2006-06-28 | 南京工业大学 | Process of micro electrolysis pretreating PTA waste water |
| CN102050508A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Sewage treatment method for circulating cooling water system |
| CN102976532A (en) * | 2012-12-28 | 2013-03-20 | 湘潭大学 | Method for treating fluorine-containing polymetallic acidic smelting wastewater by internal electrolysis and coprecipitation of ferric-carbon |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496077A (en) * | 2014-12-22 | 2015-04-08 | 同济大学 | Deep scrap iron catalytic ozonation wastewater treatment method |
| CN104920465A (en) * | 2015-06-23 | 2015-09-23 | 上海金布梯环保科技发展有限公司 | Algae growth inhibiting composition and preparation method and application thereof |
| CN112811681A (en) * | 2019-11-15 | 2021-05-18 | 南京理工大学 | Zero-phosphorus discharge treatment process for circulating water phosphine system corrosion and scale inhibitor |
| CN115818850A (en) * | 2022-12-20 | 2023-03-21 | 浙江百斯特化工有限公司 | Composite phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN115818850B (en) * | 2022-12-20 | 2023-10-10 | 浙江百斯特化工有限公司 | Composite phosphorus-free corrosion and scale inhibitor and preparation method thereof |
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Application publication date: 20131204 |