CN105668748A - Method for removing organic phosphorus hydroxy ethidene diphosphonic acid in waste water - Google Patents
Method for removing organic phosphorus hydroxy ethidene diphosphonic acid in waste water Download PDFInfo
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- CN105668748A CN105668748A CN201610227840.0A CN201610227840A CN105668748A CN 105668748 A CN105668748 A CN 105668748A CN 201610227840 A CN201610227840 A CN 201610227840A CN 105668748 A CN105668748 A CN 105668748A
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- waste water
- organophosphor
- diphosphonic acid
- remove
- hydroxy ethylidene
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to a method for removing organic phosphorus hydroxy ethidene diphosphonic acid in waste water.Calcium hydroxide, ferric salt or aluminum salt and a flocculating agent solution are sequentially added into the waste water containing organic phosphorus HEDP, the organic phosphorus HEDP removing rate can reach 96% or above, and concentration of phosphorus in the solution can be reduced to be 0.5 mg/L or below.According to the method, the treatment time is short, the phosphorus removing effect is good, running operation is stable, cost is low, and the emission standard of total phosphorus in output water is met.
Description
Technical field
The present invention relates to a kind of method adopting chemical precipitation method to remove organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), belong to method of wastewater treatment field.
Background technology
Generally comprising organic phosphate and inorganic phosphate in waste water, the removal of the inorganic phosphate in waste water usually directly adds chemical agent, is translated into insoluble calcium phosphate precipitation, and then solid-liquid separation can be removed; And the method that organic phosphate adopts now is that its initial oxidation is degraded to inorganic phosphate, adds corresponding chemical medicament and remove. Wherein oxidation degradation method has the degraded of photocatalytic oxidation degradation, ozone oxidation, irradiation-induced degradation, microbial degradation, low-temperature plasma degradation etc. Such as CN101704606A discloses a kind of processing method containing organism P wastewater, the technique waste water containing organophosphor regulates pH value to 3-4, adds hydrogen peroxide and it is carried out oxidative degradation; Then passing in catalytic microelectrolyzer, add iron filings and activated carbon and stir, being electrochemically reacted, catalytic microelectrolyzer bottom blasts air, removes the hardly degraded organic substance in technique waste water; The water outlet of catalytic microelectrolyzer passes into oxidizing reactor, adds hydrogen peroxide and carries out multi-stage oxidizing process, then regulates the pH value of waste water to 8-9, is subsequently adding flocculant and precipitates, forms phosphoric acid iron salt and calcium precipitation, thus the phosphorus removed in waste water. This inventive method is organophosphor to be first converted into Phos remove, and its complex steps, equipment is complicated.
HEDP chemical name 1-hydroxy ethylidene-1,1-diphosphonic acid, molecular formula C2H8O7P2, it is a kind of conventional organophosphor acids anti-incrustation corrosion inhibitor, stable complex can be formed with ferrum, copper, zinc, calcium many kinds of metal ions, therefore purposes is very extensive. Such as, the Stability of Metal Complexes that HEDP and copper ion are formed is high, and therefore the copper coating of energy excellent can be used for copper pre-plating, referring to CN101387000A. For the method for the wastewater treatment of HEDP copper pre-plating, adopting iron filings, steel cuttings light electrolysis, flocculation sediment, calcium hydroxide precipitation, referring to CN101624244A. On the other hand, HEDP and calcium ion form six annulus chelates, thus have good scale inhibition effect, remain to play good corrosion-mitigation scale-inhibition effect, remain to very stable at a high ph, not facile hydrolysis, be not easily decomposed at 250 DEG C. Due to the anticorrosion-antiscaling property that HEDP is good, being widely used in the industrial circulating cooling water systems such as electric power, chemical industry, metallurgy, chemical fertilizer, its general working concentration is 10-50mg/L. Owing to HEDP is the organic phosphate that a kind of industry is commonly used, organic phosphorous content in waste water can be improved, cause total phosphorus concentration to exceed standard, it is therefore desirable to take corresponding measure to remove.For containing the waste water of organophosphor HEDP in a large number, minimizing technology now is that early stage needs initial oxidation to degrade, then chemical precipitation, its complex steps, is unfavorable for operation, and relatively costly.
Summary of the invention
For the complex steps of organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) minimizing technology in existing waste water and relatively costly deficiency, the present invention provides one to utilize chemical precipitation method to remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) in waste water, namely directly adds chemical reagent by the HEDP method removed.
Term illustrates:
Waste water: waste water of the present invention refers to the waste water containing organophosphor, is the waste water of 10-50mg/L containing HEDP concentration, always containing phosphorus concentration≤15mg/L.
Technical scheme is as follows:
In a kind of removal waste water, the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), comprises the following steps that
(1) in waste water, add solid calcium hydroxide, regulate the pH to 11-12 of waste water, be sufficiently stirred for and obtain suspension A;
(2) being rapidly added iron salt solutions or aluminum salt solution in suspension A, the mass ratio making ferrum or aluminum and HEDP is 10-11: 1; Stir, obtain suspension B;
(3) in suspension B, add flocculant, accelerate flocculation sediment; Stand 30-50min, discharge supernatant; Isolate precipitation to remove.
According to currently preferred, in step (1), solid calcium hydroxide obtains dosage is 0.5-0.9kg/t waste water; Preferred by the pH regulator of waste water to 12.
According to currently preferred, in step (2), it is formulated that described iron salt solutions is that ferrous sulfate adds water, and matching while using, the addition of iron salt solutions is: ferrum and HEDP mass ratio 10: 1. Preferred iron salt solutions concentration is 100g/L.
According to currently preferred, in step (2), described aluminium salt is aluminum sulfate or aluminium polychlorid, and aluminum salt solution concentration is 100-300g/L. Aluminum salt solution addition is: the mass ratio of aluminum and HEDP is about 10-11: 1. It is preferred that, aluminum sulfate solution concentration is 200-300g/L, and polymeric aluminum chlorides solution concentration is 120-160g/L.
According to currently preferred, flocculant described in step (3) is anion-polyacrylamide flocculant (PAM), and flocculant concentration is 0.8-1.2g/L. Flocculant is added in an amount of 10-40mL/L waste water, can determine consumption according to required settling velocity.
The method of the present invention carries out under normal temperature condition, and the supernatant discharged after being disposed is the waste water handled well, and pH, close to neutral, facilitates subsequent technique to process. Method of the invention is particularly suitable for the wastewater treatment of industrial circulating water containing organophosphor HEDP.
The excellent results of the present invention is as follows:
1, for mainly containing the waste water of organophosphor HEDP, it is not necessary to the oxidative degradation carrying out early stage processes, and directly adding chemical reagent can remove organophosphor, greatly reduces operating procedure, easy to operate. The present invention studies discovery, and after wastewater pH is adjusted to 11-12, the ferrous sulfate of addition can form hydrogen-oxygen ferrous precipitation with substantial amounts of hydroxyl rapidly, organophosphor HEDP absorption in water is together precipitated while precipitation; Ferrous iron is easily oxidized to ferric ion simultaneously, many multinuclear hydroxo complexes can be hydrolyzed into, these multinuclear hydroxo complexes can effectively adsorb the organophosphor HEDP in water, the Zeta potential of colloid can also be effectively reduced or eliminate simultaneously, colloid is swept and coacervating large particle under the effect such as charge neutrality at adsorption bridging, flco volume, plays good flocculating effect.
2, the present invention adopts and adds two kinds of slaine ingredient combination removal organophosphor HEDP, and the chemical reagent added is mainly calcium hydroxide and iron salt solutions or aluminum salt solution, it is easy to add, and will not introduce new pollutant, cause secondary pollution.Wastewater pH after process is close to neutral, it is simple to subsequent technique processes.
3, added chemical reagent, it is easy to obtain, and cheap, greatly reduce processing cost.
4, the method process time is short, and phosphor-removing effect is good, runs stable operation. Organophosphor HEDP clearance effect up to about 96% and more than, the phosphorus concentration in solution can be down to below 0.5mg/L. Meet the water outlet total phosphorus discharge standard of increasingly stringent.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but is not limited to this.
Waste water described in embodiment is the waste water after the industrial cycle containing organophosphor HEDP uses, and before processing, Analysis Results of Water Quality is: HEDP concentration is 40mg/L, and total phosphorus concentration is 12mg/L, pH=6.5.
Flocculant PAM described in embodiment is anion-polyacrylamide flocculant, molecular weight 600-2200 ten thousand.
Embodiment 1: removing the method for organophosphor HEDP in waste water, step is as follows:
Take 100mL waste water in beaker, under normal temperature condition, in waste water, add solid calcium hydroxide 0.052g wastewater pH is adjusted to 12, after being sufficiently stirred for, it is rapidly added the 100g/L copperas solution of 2mL matching while using, stirs, it is subsequently adding the PAM of 1mL1g/L, accelerates flocculation sediment. After standing 30min, precipitation in solution being filtered, the supernatant of discharge is the waste water handled well, and recording phosphorus concentration is 0.493mg/L, and clearance is 95.9%.
Embodiment 2: removing the method for organophosphor HEDP in waste water, step is as follows:
Taking 100mL waste water in beaker, under normal temperature condition, adding solid calcium hydroxide 0.078g in waste water can be adjusted to 12 by wastewater pH, after being sufficiently stirred for, it is rapidly added the 250g/L aluminum sulfate solution of 2mL matching while using, stirs, it is subsequently adding the PAM of 1mL1g/L, accelerates flocculation sediment. After standing 30min, precipitation in solution being filtered, the supernatant of discharge is the waste water handled well, and recording phosphorus concentration is 0.417mg/L, and clearance is 96.5%.
Embodiment 3: removing the method for organophosphor HEDP in waste water, step is as follows:
Taking 100mL waste water in beaker, under normal temperature condition, adding solid calcium hydroxide 0.083g in waste water can be adjusted to 12 by wastewater pH, after being sufficiently stirred for, it is rapidly added the 142g/L polymeric aluminum chlorides solution of 2mL matching while using, stirs, it is subsequently adding the PAM of 3mL1g/L, accelerates flocculation sediment. After standing 30min, precipitation in solution being filtered, the supernatant of discharge is the waste water handled well, and recording phosphorus concentration is 0.488mg/L, and clearance is 96%.
Claims (8)
1. remove a method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, comprise the following steps that
(1) in waste water, add solid calcium hydroxide, regulate the pH to 11-12 of waste water, be sufficiently stirred for and obtain suspension A;
(2) being rapidly added iron salt solutions or aluminum salt solution in suspension A, the mass ratio making ferrum or aluminum and HEDP is 10-11:1; Stir, obtain suspension B;
(3) in suspension B, add flocculant, accelerate flocculation sediment; Stand 30-50min, discharge supernatant; Isolate precipitation to remove.
2. according to claim 1 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterised in that in step (1), solid calcium hydroxide obtains dosage is 0.5-0.9kg/t waste water; Preferred by the pH regulator of waste water to 12.
3. according to claim 1 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterized in that, in step (2), it is formulated that described iron salt solutions is that ferrous sulfate adds water, matching while using, the addition of iron salt solutions is: ferrum and ATMP mass ratio 10:1.
4. a kind of according to claim 1 or 3 removes the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterised in that iron salt solutions concentration is 100g/L.
5. according to claim 1 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterised in that in step (2), described aluminium salt is aluminum sulfate or aluminium polychlorid, and aluminum salt solution concentration is 100-300g/L.
6. according to claim 5 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterised in that in step (2), described aluminum sulfate solution concentration is 200-300g/L, and polymeric aluminum chlorides solution concentration is 120-160g/L.
7. according to claim 1 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterized in that, flocculant described in step (3) is anion-polyacrylamide flocculant (PAM), and flocculant concentration is 0.8-1.2g/L.
8. according to claim 1 a kind of remove the method for organophosphor 1-hydroxy ethylidene-1,1-diphosphonic acid in waste water, it is characterised in that flocculant described in step (3) is added in an amount of 10-40mL/L waste water.
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| CN201610227840.0A CN105668748B (en) | 2016-04-13 | 2016-04-13 | A kind of method of organic phosphorus 1-hydroxy ethylidene-1,1-diphosphonic acid in removal waste water |
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| CN201610227840.0A CN105668748B (en) | 2016-04-13 | 2016-04-13 | A kind of method of organic phosphorus 1-hydroxy ethylidene-1,1-diphosphonic acid in removal waste water |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5765380A (en) * | 1980-10-09 | 1982-04-20 | Toray Ind Inc | Removal of phosphorus from waste water |
| CN101704606A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Treatment method of waste water containing organic phosphorus |
| CN104291420A (en) * | 2014-09-11 | 2015-01-21 | 陕西省石油化工研究设计院 | Phosphorus removing agent containing inorganic mineral and application method thereof |
-
2016
- 2016-04-13 CN CN201610227840.0A patent/CN105668748B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5765380A (en) * | 1980-10-09 | 1982-04-20 | Toray Ind Inc | Removal of phosphorus from waste water |
| CN101704606A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Treatment method of waste water containing organic phosphorus |
| CN104291420A (en) * | 2014-09-11 | 2015-01-21 | 陕西省石油化工研究设计院 | Phosphorus removing agent containing inorganic mineral and application method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李肖琳等: "有机磷水处理药剂生产废水处理技术的研究", 《工业水处理》 * |
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