CN102464386A - Complexing agent for removing vanadium in wastewater and application method thereof - Google Patents
Complexing agent for removing vanadium in wastewater and application method thereof Download PDFInfo
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- CN102464386A CN102464386A CN2011103207560A CN201110320756A CN102464386A CN 102464386 A CN102464386 A CN 102464386A CN 2011103207560 A CN2011103207560 A CN 2011103207560A CN 201110320756 A CN201110320756 A CN 201110320756A CN 102464386 A CN102464386 A CN 102464386A
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- vanadium
- recombiner
- complexing agent
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Abstract
The invention discloses a complexing agent for removing vanadium in wastewater and an application method thereof, which belong to the field of wastewater treatment in environment protection. The complexing agent disclosed by the invention is prepared by compounding the following components in percentage by weight: 5-10% of inorganic salt, 10-20% of metal oxide, 10-25% of quaternary ammonium salt and 50-70% of inorganic mineral. The application method comprises the steps of: adding the prepared complexing agent into the wastewater containing vanadium with the concentration of 10-400mg/L, wherein the weight ratio of the added complexing agent to the wastewater is 1:20 to 1:200; stirring for 1-2h, standing and depositing; and separating mud and water so as to reduce the concentration of the vanadium in the yielding water to below 1.0mg/L. The complexing agent and the application method thereof disclosed by the invention have the characteristics of wide material source range, low price, smaller dosage of chemical agent, low running expense, no secondary pollution in a treatment process, high vanadium removal efficiency, good effect, and the like; and the removal rate can reach above 99.9%.
Description
Technical field
The present invention is a kind of recombiner and application method thereof of removing vanadium in the waste water, relates to the removal of vanadium in the industry waste water such as machinery, automobile, shipbuilding, railway, bridge, belongs to field of waste water treatment in the environment protection.
Background technology
Vanadium is a kind of important alloying element; Be mainly used in Iron And Steel Industry; Be widely used in industries such as machinery, automobile, shipbuilding, railway, bridge, in addition, catalyzer, pigment, paint, glass and the Production of Ceramics that also is widely used in preparation iron alloy, chemical reaction is with additive etc.The compound of many vanadium is all toxic; If human body sucks too much vanadium; Can cause the infringement of respiratory system, gastro-intestinal system, neural system, hemopoietic system; The activity that also can suppress apysase and Phosphoric acid esterase makes skin inflammation occur and causes the abnormalism pathology, and to surpass 10mg/L promptly harmful for the content of vanadium in the farm crop.Along with the vanadium industrial expansion, vanadium-containing water is polluted underground water more, influences human beings'health, and therefore, country has put into effect " vanadium emission of industrial pollutants standard ", and vanadium in the waste water has been done restriction, and its limit value is 1.0mg/L.
At present, in the vanadium-containing water process field, main improvement method has the ferrous sulfate precipitator method, the iron filings precipitator method, sulfurous gas method, ion exchange method, electrolytic process both at home and abroad.Ferrous sulfate precipitator method equipment is simple, and treatment capacity is big, and vanadium removal is effective, on engineering, obtained certain application, but consumption is big, and the treating processes quantity of slag is big.The treatment of wastes with processes of wastes against one another of iron filings precipitator method ability, processing cost is low, but is prone to produce the corrosion and passivation phenomenon of iron filings, and the water treatment effect is unstable.The sulfurous gas method has realized the recycling of vanadium, but the source problem that comes of sulfurous gas has seriously limited the practical ranges of this kind method.The recyclable vanadium of ion exchange method, treatment effect is more stable, but the ion exchange resin large usage quantity, regeneration is frequent, and processing cost is higher, is applicable to from the lower concentration vanadium solution to reclaim vanadium.Notification number is that CN86106414 discloses the method that a kind of electrolytic process is handled wastewater containing vanadium and chromium, and the water quality after this method is handled is good, recyclable vanadium, but occupation area of equipment is big, and one-time investment is high.
Recombiner of the present invention has overcome the deficiency of prior art; When handling the waste water of vanadium concentration at 10～400mg/L; Clearance all reaches more than 99.9%; Be applicable to the vanadium-containing water of handling low middle and high concentration, have remarkable economic efficiency and social benefit, have good application prospects in the vanadium-containing water process field.
Summary of the invention
The objective of the invention is for overcoming the deficiency of prior art, a kind of recombiner and application method thereof of removing vanadium in the waste water is provided, it is extensive that the present invention has raw material sources; Cheap, added amount of chemical is less relatively, and working cost is low; The treating processes non-secondary pollution; It is high to remove vanadium efficient, and effective, clearance can reach 99.9% with first-class characteristics.
The technical scheme that the present invention adopts is: recombiner of the present invention be by inorganic salt, MOX, quaternary ammonium salt, inorganic mineral is composite forms, wherein the mass percent of each composition is respectively inorganic salt 5%～10%, MOX 10%～20%, quaternary ammonium salt 10%～25%, inorganic mineral 50%～70%.
Described inorganic salt are meant one or both in potassium pyrosulfite, cuprous chloride, cuprous sulfate, the aluminum chloride.
Described MOX is meant one or both in aluminum oxide, sodium oxide, the Natural manganese dioxide.
Described quaternary ammonium salt is meant one or both in tri-n-octyl methyl ammonium chloride, palmityl trimethyl ammonium chloride, Tetrabutyl amonium bromide, the 3-ethyl benzyl ammonium chloride.
Described inorganic mineral is meant one or both in rectorite leng, kaolin, the phosphatic rock.
Each material mass accounts for the recombiner total mass ratio: potassium pyrosulfite 2%～10%, cuprous chloride 3%～10%, cuprous sulfate 4%～10%, aluminum chloride 2%～10%; Aluminum oxide 5%～20%, sodium oxide 5%～20%, Natural manganese dioxide 5%～20%; Tri-n-octyl methyl ammonium chloride 10%～25%, palmityl trimethyl ammonium chloride 5%～25%, Tetrabutyl amonium bromide 7%～25%, 3-ethyl benzyl ammonium chloride 8%～25%; Rectorite leng 20%～70%, kaolin 25%～70%, phosphatic rock 25%～70%.
The compound process of recombiner of the present invention is following:
(1) cross 80～100 mesh sieves after will accounting for 50%～70% inorganic mineral fragmentation of recombiner total mass, again with behind the deionized water wash five times in 105 ° of C oven dry down;
(2) quaternary ammonium salt of corresponding proportion is water-soluble, add the above-mentioned inorganic mineral after oven dry, stirred 30～45 minutes, leave standstill and soaked 1～2 hour;
(3) in above-mentioned mixed solution, add the inorganic salt of corresponding proportion again, stirred 40～60 minutes, leave standstill immersion 1～2 hour, at 70～80 ° of C, evaporate to dryness is removed redundant moisture;
(4) above-mentioned powder mixture is pulverized once more, crossed 80～100 mesh sieves, add MOX, stir, mix, promptly get recombiner of the present invention.
Application method of the present invention is:
The recombiner that aforementioned proportion is made joins vanadium concentration in the waste water of 10～400mg/L; The recombiner that adds and the mass ratio of waste water are 1:20～1:200, stir 1～2 hour, staticly settle; Mud-water separation can make water outlet vanadium concentration drop to below the 1.0mg/L.
Embodiment
Recombiner of the present invention be by inorganic salt, MOX, quaternary ammonium salt, inorganic mineral is composite forms, wherein the mass percent of each composition is respectively inorganic salt 5%～10%, MOX 10%～20%, quaternary ammonium salt 10%～25%, inorganic mineral 50%～70%.
Described inorganic salt are meant one or both in potassium pyrosulfite, cuprous chloride, cuprous sulfate, the aluminum chloride.
Described MOX is meant one or both in aluminum oxide, sodium oxide, the Natural manganese dioxide.
Described quaternary ammonium salt is meant one or both in tri-n-octyl methyl ammonium chloride, palmityl trimethyl ammonium chloride, Tetrabutyl amonium bromide, the 3-ethyl benzyl ammonium chloride.
Described inorganic mineral is meant one or both in rectorite leng, kaolin, the phosphatic rock.
Each material mass accounts for the recombiner total mass ratio: potassium pyrosulfite 2%～10%, cuprous chloride 3%～10%, cuprous sulfate 4%～10%, aluminum chloride 2%～10%; Aluminum oxide 5%～20%, sodium oxide 5%～20%, Natural manganese dioxide 5%～20%; Tri-n-octyl methyl ammonium chloride 10%～25%, palmityl trimethyl ammonium chloride 5%～25%, Tetrabutyl amonium bromide 7%～25%, 3-ethyl benzyl ammonium chloride 8%～25%; Rectorite leng 20%～70%, kaolin 25%～70%, phosphatic rock 25%～70%.
The recombiner that aforementioned proportion is made joins vanadium concentration in the waste water of 10～400mg/L; The recombiner that adds and the mass ratio of waste water are 1:20～1:200, stir 1～2 hour, staticly settle; Mud-water separation, water outlet can make that vanadium concentration drops to below the 1.0mg/L in the waste water.
Instance 1
By mass percentage, get rectorite leng 70%, 3-ethyl benzyl ammonium chloride 15%, cuprous sulfate 5%, aluminum oxide 10% and be made into recombiner, the vanadium-containing water of certain machine works is handled through compound process of the present invention; Added amount of chemical is 5ppm; Stirred 1 hour, and staticly settled mud-water separation; The concentration of vanadium has dropped to 0.02mg/L from 25mg/L in the waste water, and the vanadium clearance has reached 99.92%.
Instance 2
By mass percentage, get rectorite leng 40%, kaolin 25%, Tetrabutyl amonium bromide 15%, potassium pyrosulfite 10%, sodium oxide 10% and be made into recombiner, the vanadium-containing water of certain automobile factory is handled through compound process of the present invention; Added amount of chemical is 9ppm; Stirred 1 hour, and staticly settled mud-water separation; The concentration of vanadium has dropped to 0.05mg/L from 115mg/L in the waste water, and the vanadium clearance has reached 99.96%.
Instance 3
By mass percentage, get kaolin 50%, tri-n-octyl methyl ammonium chloride 10%, palmityl trimethyl ammonium chloride 10%, cuprous chloride 10%, aluminum oxide 10%, Natural manganese dioxide 10% and be made into recombiner, the vanadium-containing water of certain automobile factory is handled through compound process of the present invention; Added amount of chemical is 13ppm; Stirred 1 hour, and staticly settled mud-water separation; The concentration of vanadium has dropped to 0.05mg/L from 175mg/L in the waste water, and the vanadium clearance has reached 99.97%.
Instance 4
By mass percentage, get phosphatic rock 65%, Tetrabutyl amonium bromide 7%, 3-ethyl benzyl ammonium chloride 8%, cuprous chloride 7%, aluminum chloride 3%, Natural manganese dioxide 10%, be made into recombiner through compound process of the present invention; Vanadium-containing water to certain yard is handled, and added amount of chemical is 18ppm, stirs 2 hours; Staticly settle; Mud-water separation, the concentration of vanadium has dropped to 0.1mg/L from 245mg/L in the waste water, and the vanadium clearance has reached 99.96%.
Instance 5
By mass percentage, get rectorite leng 20%, phosphatic rock 50%, Tetrabutyl amonium bromide 7%, palmityl trimethyl ammonium chloride 5%, cuprous chloride 5%, aluminum chloride 3%, sodium oxide 10%, be made into recombiner through compound process of the present invention; Vanadium-containing water to certain yard is handled, and added amount of chemical is 25ppm, stirs 2 hours; Staticly settle; Mud-water separation, the concentration of vanadium has dropped to 0.3mg/L from 375mg/L in the waste water, and the vanadium clearance has reached 99.92%.
Claims (5)
1. recombiner of removing vanadium in the waste water; It is characterized in that: be by inorganic salt, MOX, quaternary ammonium salt, inorganic mineral is composite forms, wherein the mass percent of each composition is respectively inorganic salt 5%～10%, MOX 10%～20%, quaternary ammonium salt 10%～25%, inorganic mineral 50%～70%.
2. a kind of recombiner of removing vanadium in the waste water according to claim 1, it is characterized in that: described inorganic salt are meant one or both in Sodium Pyrosulfite, cuprous chloride, cuprous sulfate, the aluminum chloride.
3. a kind of recombiner of removing vanadium in the waste water according to claim 1, it is characterized in that: described MOX is meant one or both in aluminum oxide, sodium oxide, the Natural manganese dioxide.
4. a kind of recombiner of removing vanadium in the waste water according to claim 1, it is characterized in that: described quaternary ammonium salt is meant one or both in tri-n-octyl methyl ammonium chloride, palmityl trimethyl ammonium chloride, Tetrabutyl amonium bromide, the 3-ethyl benzyl ammonium chloride.
5. a kind of recombiner of removing vanadium in the waste water according to claim 1, it is characterized in that: described inorganic mineral is meant one or both in rectorite leng, kaolin, the phosphatic rock.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103207560A CN102464386A (en) | 2011-10-20 | 2011-10-20 | Complexing agent for removing vanadium in wastewater and application method thereof |
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| CN2011103207560A CN102464386A (en) | 2011-10-20 | 2011-10-20 | Complexing agent for removing vanadium in wastewater and application method thereof |
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| CN102464386A true CN102464386A (en) | 2012-05-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967352A (en) * | 2016-07-13 | 2016-09-28 | 安徽天顺环保设备股份有限公司 | Industrial wastewater high-efficiency treating agent and preparation method thereof |
| CN106396170A (en) * | 2016-10-19 | 2017-02-15 | 浙江省农业科学院 | Aeration-free waste water air floatation complexing agent and its preparation method, use method and use device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0140088A2 (en) * | 1983-09-29 | 1985-05-08 | Treibacher Chemische Werke Aktiengesellschaft | Process for recovering vanadium from waste water |
| CN101113062A (en) * | 2006-07-27 | 2008-01-30 | 边绍贵 | Vanadium-containing sewage treatment method |
-
2011
- 2011-10-20 CN CN2011103207560A patent/CN102464386A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0140088A2 (en) * | 1983-09-29 | 1985-05-08 | Treibacher Chemische Werke Aktiengesellschaft | Process for recovering vanadium from waste water |
| CN101113062A (en) * | 2006-07-27 | 2008-01-30 | 边绍贵 | Vanadium-containing sewage treatment method |
Non-Patent Citations (3)
| Title |
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| 司士辉,李凌璞,王树国: "硫酸亚铁改性沸石对废水中钒（V)的吸附研究", 《黄石理工学院学报》, vol. 25, no. 3, 30 June 2009 (2009-06-30), pages 7 - 10 * |
| 朱寿川: "还原一中和+蒸发浓缩工艺处理沉钒废水的工程应用", 《工业水处理》, vol. 29, no. 9, 30 September 2009 (2009-09-30), pages 84 - 87 * |
| 黄韵等: "改性累托石对水溶液中Cr(VI)的吸附", 《硅酸盐学报》, vol. 33, no. 2, 28 February 2005 (2005-02-28), pages 197 - 201 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967352A (en) * | 2016-07-13 | 2016-09-28 | 安徽天顺环保设备股份有限公司 | Industrial wastewater high-efficiency treating agent and preparation method thereof |
| CN106396170A (en) * | 2016-10-19 | 2017-02-15 | 浙江省农业科学院 | Aeration-free waste water air floatation complexing agent and its preparation method, use method and use device |
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Application publication date: 20120523 |