CN108640332B - Method and device for treating hypophosphorous acid and phosphorous in wastewater - Google Patents
Method and device for treating hypophosphorous acid and phosphorous in wastewater Download PDFInfo
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- CN108640332B CN108640332B CN201810376386.4A CN201810376386A CN108640332B CN 108640332 B CN108640332 B CN 108640332B CN 201810376386 A CN201810376386 A CN 201810376386A CN 108640332 B CN108640332 B CN 108640332B
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Water Treatment By Sorption (AREA)
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Abstract
The invention belongs to the field of environment functional materials, and particularly relates to a method and a device for treating hypophosphorous acid and phosphorous in wastewater, wherein the method specifically comprises the following steps: adding hydrogen peroxide into wastewater containing hypophosphorous acid and phosphorous to carry out pre-oxidation so as to convert the hypophosphorous acid into phosphorous; after pre-oxidation, magnesium-aluminum layered composite oxide is added to adsorb phosphorous. The device comprises a pre-oxidation reaction tank, an adsorption reaction tank, a hydrogen peroxide injection part and a magnesium-aluminum layered composite oxide putting part, wherein the hydrogen peroxide injection part injects hydrogen peroxide into the pre-oxidation reaction tank to perform pre-oxidation reaction, and the putting part puts the magnesium-aluminum layered composite oxide into the adsorption reaction tank to adsorb phosphite radicals. The invention utilizes hydrogen peroxide to convert the phosphorous into phosphorous and utilizes the excellent adsorption property of calcined hydrotalcite on the phosphorous to realize the novel and efficient treatment of the phosphorous wastewater, and has important significance for the treatment of the electroplating phosphorous wastewater which is difficult to treat.
Description
Technical Field
The invention belongs to the field of environment functional materials, and particularly relates to a method and a device for treating hypophosphorous acid and phosphorous in wastewater.
Background
In the electroplating industry, a large amount of phosphate with a low valence state is usually added for better electroplating effect, and the use of a large amount of sodium hypophosphite as a reducing agent can cause a large amount of hypophosphorous phosphate in wastewater, so that the effect of directly adding calcium, iron and other ions on the precipitation of the hypophosphite is not good. The treatment of the wastewater containing phosphorus and phosphorous is always a difficult problem in the treatment of electroplating wastewater in China.
The conventional phosphorous wastewater treatment technology utilizes advanced oxidation technology, such as UV/H2O2Method of whichAfter the phosphorous phosphorus is converted into the orthophosphoric phosphorus, lime or calcium salt and the like are added to convert the orthophosphoric phosphorus into the precipitate (P.Liu, C.L.Li, X.G.Liang, J.H.Xu, G.Lu, F.Ji.advanced Oxidation of Hypophosphosite and phosphor by A UV/H2O2Process). However, the advanced oxidation technology has the disadvantages of low efficiency, easy generation of a large amount of iron sludge combined with the precipitate to form secondary polluted sludge, and the like, and the treatment cost of the advanced oxidation technology makes the treatment method not practical to be popularized.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method and a device for treating hypophosphorous acid and phosphorous in wastewater.
The purpose of the invention is realized by the following technical scheme:
a method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
adding hydrogen peroxide into wastewater containing hypophosphorous acid and phosphorous to carry out pre-oxidation so as to convert the hypophosphorous acid into phosphorous; after pre-oxidation, magnesium-aluminum layered composite oxide is added to adsorb phosphorous.
Preferably, the mass ratio of the magnesium-aluminum layered composite oxide to the total amount of the hypophosphorous acid and the phosphorous in the wastewater is 30-4000: 1.
preferably, the pre-oxidation is: adding a hydrogen peroxide solution, uniformly stirring, and fully pre-oxidizing for 10-30 min.
More preferably, the mass ratio of the hydrogen peroxide to the hypophosphorous acid in the wastewater is 800-2000: 1.
preferably, the adsorption is: stirring the magnesium-aluminum layered composite oxide in the adding process, and then standing for 0.5-3 h. More preferably, the stirring is performed for 4-6 hours at 150-250 r/min.
Preferably, the magnesium-aluminum layered composite oxide is prepared by the following method:
and calcining the magnesium-aluminum hydrotalcite at 400-500 ℃ for 4-5 h, cooling, grinding and sieving to obtain the magnesium-aluminum layered composite oxide.
More preferably, the sieving is 180-200 mesh sieving.
The utility model provides a handle device of inferior phosphorus and phosphorous in waste water, includes pre-oxidation reaction pond, adsorption reaction pond, hydrogen peroxide injection portion, magnesium aluminium stratiform composite oxide portion of puting in, wherein, hydrogen peroxide injection portion injects hydrogen peroxide in order to carry out the pre-oxidation reaction to the pre-oxidation reaction pond, the portion of puting in puts in magnesium aluminium stratiform composite oxide in to the adsorption reaction pond to carry out the absorption of phosphite.
Preferably, the pre-oxidation reaction tank and the adsorption reaction tank both comprise stirring members.
The principle of the invention is as follows:
hydrogen peroxide is a strong oxidant, and is often combined with ferrous ions as a Fenton reagent to be applied to advanced oxidation, but a large amount of iron sludge is generated, and in the case of electroplating wastewater, the iron sludge also contains a large amount of heavy metals, and belongs to dangerous waste. However, hydrogen peroxide by itself can readily oxidize hypophosphite to phosphite (H)2PO2 -+3OH-＝HPO3 2-+2H2O+2e-，Eθ1.65V) used in phosphorous acid wastewater to convert hypophosphite in wastewater into phosphite.
Magnesium aluminum hydrotalcite (hydrotalcite) belongs to an anionic layered compound and is characterized by intercalation and interchangeability of interlayer anions. The magnalium hydrotalcite is calcined at a specific temperature and loses interlayer anions to generate a bimetal composite oxide, the calcined magnalium hydrotalcite has a memory effect, and the magnalium hydrotalcite is put into a solution containing specific anions to be calcined and can be recovered to the magnalium hydrotalcite with an ordered interlayer structure by absorbing the anions in the solution.
The magnesium-aluminum layered composite oxide obtained after calcination can be added into phosphorous wastewater to achieve efficient phosphorous removal, which is found for the first time.
Compared with the prior art, the invention has the following advantages and effects:
1. the method can realize efficient phosphorus removal (the removal rate is more than 95%) on the phosphorus and phosphorus wastewater by only using a small amount of adsorbent (magnesium-aluminum layered composite oxide: phosphorus and phosphorus is 30: 1).
2. The invention has low requirement on the oxidation process of phosphorus, only needs to convert the hypophosphorous acid into the phosphorous without further oxidizing the hypophosphorous acid and the phosphorous into the orthophosphoric acid, not only saves the using amount of the oxidant, but also improves the oxidation efficiency of the phosphorus.
3. The invention has the advantages of simple and convenient material preparation, low preparation cost, good treatment effect on the phosphorus wastewater, simple and easy method, low treatment cost and convenient large-scale popularization and application.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
The phosphorous wastewater described in the following examples means wastewater having a total phosphorous concentration of about 10 to 40mg/L (phosphorous concentration of 7.5 to 22.5mg/L, phosphorous concentration of 2.5 to 7.5mg/L) and a nickel ion concentration of about 10 mg/L.
Example 1
A method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
(1) placing the magnesium-aluminum hydrotalcite in a crucible, calcining for 4 hours in a muffle furnace at 400 ℃, cooling, grinding and sieving with a 200-mesh sieve to obtain a magnesium-aluminum layered composite oxide;
(2) injecting 20 ml/L30% hydrogen peroxide solution into an oxidation reaction tank (wastewater with the sub-phosphorus concentration of 7.5mg/L, the phosphorous concentration of 2.5mg/L and the nickel ion concentration of about 10 mg/L), stirring, and transferring the wastewater into an adsorption reaction tank after 10min of full pre-oxidation;
(3) and (3) adding 20g/L of the magnesium-aluminum layered composite into the adsorption reaction tank through a magnesium-aluminum layered composite oxide adding part, stirring for 4 hours at 200r/min by using a stirring component to fully react, and standing for 1 hour to obtain treated tail water.
Example 2
A method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
(1) placing the magnesium-aluminum hydrotalcite in a crucible, calcining for 4 hours in a muffle furnace at 500 ℃, cooling, grinding and sieving with a 200-mesh sieve to obtain a magnesium-aluminum layered composite oxide;
(2) injecting 40 ml/L30% hydrogen peroxide solution into an oxidation reaction tank (wastewater with the sub-phosphorus concentration of 7.5mg/L, the phosphorous concentration of 2.5mg/L and the nickel ion concentration of about 10 mg/L), stirring, and transferring the wastewater into an adsorption reaction tank after 10min of full pre-oxidation;
(3) and (3) adding 20g/L of the magnesium-aluminum layered composite into the adsorption reaction tank through a magnesium-aluminum layered composite oxide adding part, stirring for 4 hours at 200r/min by using a stirring component to fully react, and standing for 1 hour to obtain treated tail water.
Example 3
A method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
(1) placing the magnesium-aluminum hydrotalcite in a crucible, calcining for 4 hours in a muffle furnace at 500 ℃, cooling, grinding and sieving with a 200-mesh sieve to obtain a magnesium-aluminum layered composite oxide;
(2) injecting 40 ml/L30% hydrogen peroxide solution into an oxidation reaction tank (wastewater with the sub-phosphorus concentration of 7.5mg/L, the phosphorous concentration of 2.5mg/L and the nickel ion concentration of about 10 mg/L), stirring, and transferring the wastewater into an adsorption reaction tank after 10min of full pre-oxidation;
(3) and (3) adding 40g/L of the magnesium-aluminum layered composite into the adsorption reaction tank through a magnesium-aluminum layered composite oxide adding part, stirring for 4 hours at 200r/min by using a stirring component to fully react, and standing for 1 hour to obtain treated tail water.
Example 4
A method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
(1) placing the magnesium-aluminum hydrotalcite in a crucible, calcining for 4 hours in a muffle furnace at 500 ℃, cooling, grinding and sieving with a 200-mesh sieve to obtain a magnesium-aluminum layered composite oxide;
(2) injecting 120 ml/L30% hydrogen peroxide solution into an oxidation reaction tank (wastewater with the sub-phosphorus concentration of 22.5mg/L, the phosphorous concentration of 7.5mg/L and the nickel ion concentration of about 10 mg/L), stirring, and transferring the wastewater into an adsorption reaction tank after 10min of full pre-oxidation;
(3) and (3) adding 10g/L of the magnesium-aluminum layered compound into the adsorption reaction tank through a magnesium-aluminum layered compound oxide adding part, stirring for 4 hours at 200r/min by using a stirring component to fully react, and standing for 1 hour to obtain treated tail water.
Comparative example 1
A method for treating hypophosphorous and phosphorous in wastewater comprises the following steps:
(1) placing the magnesium-aluminum hydrotalcite in a crucible, calcining for 4 hours in a muffle furnace at 500 ℃, cooling, grinding and sieving with a 200-mesh sieve to obtain a magnesium-aluminum layered composite oxide;
(2) injecting 120 ml/L30% hydrogen peroxide solution into an oxidation reaction tank (wastewater with the sub-phosphorus concentration of 22.5mg/L, the phosphorous concentration of 7.5mg/L and the nickel ion concentration of about 10 mg/L), stirring, and transferring the wastewater into an adsorption reaction tank after 10min of full pre-oxidation;
(3) and (3) feeding 0.5g/L of the magnesium-aluminum layered composite into an adsorption reaction tank through a magnesium-aluminum layered composite oxide feeding part, stirring for 4 hours at 200r/min by using a stirring component to fully react, and standing for 1 hour to obtain treated tail water.
The total phosphorus content of the wastewater before and after treatment in examples 1 to 4 and comparative example 1 was measured, and the removal rate was calculated, with the results shown in table 1:
TABLE 1 Total phosphorus index before and after wastewater treatment
As can be seen from the above, the method of the invention can realize efficient phosphorus removal on the phosphorus wastewater, and the magnesium-aluminum layered composite oxide: when the total phosphorus is about 30:1, the total phosphorus removal rate of over 95 percent can be achieved for the wastewater with high phosphorus concentration of 30mg/L, and when the dosage proportion of the adsorbent is further increased, the adsorption effect is slightly improved, but the adsorption effect is not obvious, so that the phosphorus adsorption is basically balanced under the dosage proportion of 30: 1. And magnesium-aluminum layered composite oxide: when the total phosphorus is less than 30:1, the adsorption amount of phosphorus is greatly reduced, and when the ratio is about 15:1, the adsorption rate is only less than 50%, and at this time, the adsorption of phosphorus does not reach a saturation state due to the insufficient amount of the adsorbent. Therefore, the better dephosphorization effect can be achieved only within the dosage range of the adsorbent limited by the invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for treating hypophosphorous acid and phosphorous in wastewater is characterized by comprising the following steps:
adding hydrogen peroxide into wastewater containing hypophosphorous acid and phosphorous to carry out pre-oxidation so as to convert the hypophosphorous acid into phosphorous; after pre-oxidation, magnesium-aluminum layered composite oxide is added to adsorb phosphorous.
2. The method for treating the hypophosphorous acid and the phosphorous in the wastewater as claimed in claim 1, wherein the mass ratio of the magnesium-aluminum layered composite oxide to the total amount of the hypophosphorous acid and the phosphorous in the wastewater is 30-4000: 1.
3. the method of claim 1, wherein the pre-oxidation is performed by: adding a hydrogen peroxide solution, uniformly stirring, and fully pre-oxidizing for 10-30 min.
4. The method for treating the hypophosphorous acid and phosphorous in the wastewater according to claim 3, wherein the mass ratio of the hydrogen peroxide to the hypophosphorous acid in the wastewater is 800-2000: 1.
5. the method of claim 1, wherein the adsorption is: stirring the magnesium-aluminum layered composite oxide in the adding process, and then standing for 0.5-3 h.
6. The method for treating hypophosphorous and phosphorous in wastewater according to claim 5, wherein the stirring is performed at 150-250 r/min for 4-6 h.
7. The method for treating hypophosphorous and phosphorous in wastewater according to claim 1, wherein the magnesium-aluminum layered composite oxide is prepared by the following method:
and calcining the magnesium-aluminum hydrotalcite at 400-500 ℃ for 4-5 h, cooling, grinding and sieving to obtain the magnesium-aluminum layered composite oxide.
8. The method for treating the hypophosphorous and phosphorous in the wastewater according to claim 7, wherein the sieving is performed by a 180-200 mesh sieve.
9. The utility model provides a handle device of inferior phosphorus and phosphorous in waste water which characterized in that: the treatment object is wastewater containing hypophosphorous and phosphorous, and comprises a pre-oxidation reaction tank, an adsorption reaction tank, a hydrogen peroxide injection part and a magnesium-aluminum layered composite oxide feeding part; the hydrogen peroxide injection part is used for injecting hydrogen peroxide into the pre-oxidation reaction tank to perform pre-oxidation reaction so as to convert the hypophosphorous acid in the wastewater into phosphorous; the feeding part is used for feeding magnesium-aluminum layered composite oxide into the adsorption reaction tank to adsorb phosphite.
10. The apparatus of claim 9 for treating hypophosphorous and phosphorous in wastewater, comprising: the pre-oxidation reaction tank and the adsorption reaction tank both comprise stirring parts.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269870A (en) * | 2008-01-08 | 2008-09-24 | 上海大学 | Method for removing inorganic phosphorus in wastewater |
| CN101422719A (en) * | 2008-11-24 | 2009-05-06 | 哈尔滨工程大学 | Magnetic composite oxides preparation method and use of magnetic composite oxides as anionic pollutant absorbent |
| CN101830536A (en) * | 2009-03-13 | 2010-09-15 | 株式会社东芝 | Adsorption apparatus of drained water |
| WO2017160584A1 (en) * | 2016-03-17 | 2017-09-21 | Saudi Arabian Oil Company | High temperature layered mixed-metal oxide materials with enhanced stability |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269870A (en) * | 2008-01-08 | 2008-09-24 | 上海大学 | Method for removing inorganic phosphorus in wastewater |
| CN101422719A (en) * | 2008-11-24 | 2009-05-06 | 哈尔滨工程大学 | Magnetic composite oxides preparation method and use of magnetic composite oxides as anionic pollutant absorbent |
| CN101830536A (en) * | 2009-03-13 | 2010-09-15 | 株式会社东芝 | Adsorption apparatus of drained water |
| WO2017160584A1 (en) * | 2016-03-17 | 2017-09-21 | Saudi Arabian Oil Company | High temperature layered mixed-metal oxide materials with enhanced stability |
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