CN109052731A - A method of efficiently removing antimony from dyeing waste water - Google Patents

A method of efficiently removing antimony from dyeing waste water Download PDF

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Publication number
CN109052731A
CN109052731A CN201811075557.6A CN201811075557A CN109052731A CN 109052731 A CN109052731 A CN 109052731A CN 201811075557 A CN201811075557 A CN 201811075557A CN 109052731 A CN109052731 A CN 109052731A
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waste water
antimony
dyeing waste
pretreatment fluid
added
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CN109052731B (en
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朱和林
李彬
胡立华
徐飞
张志鹏
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Kaiyuan Environmental Technology Group Co.,Ltd.
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HANGZHOU KAIYUAN ENVIRONMENTAL PROTECTION ENGINEERING Co Ltd
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • 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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/20—Heavy metals or heavy metal 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
    • 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
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The present invention relates to techniques of Dyeing Wastewater Treatment fields, for there is a problem of that excessive antimony causes discharge of wastewater exceeded in dyeing waste water, disclose a kind of method that antimony is efficiently removed from dyeing waste water, the following steps are included: filtering dyeing waste water obtains pretreatment fluid, it adjusts pretreatment fluid acidity and Fenton reagent reaction is added, pretreatment fluid pH is adjusted to generating floccule, flocculant is added and stirs flocculation reaction, pretreatment fluid is sent into separation dross and aqueous in air-floating apparatus and obtains the printing and dyeing recycle-water of removing antimony, it is preferably added to modified wood fibre element and the filtering of rice husk adsorption layer simultaneously.The method of the present invention removes removal organic polluter using Fenton's reaction first, then the heavy metal ion such as antimony and a small amount of copper, chromium, zinc are removed using the iron hydroxide and flocculant that generate, it is improved by organic pollutant removal and heavy metal ion treatment by stages except antimony specificity, the antimony in dyeing waste water is effectively removed, and COD concentration and other concentration of heavy metal ion is greatly reduced.

Description

A method of efficiently removing antimony from dyeing waste water
Technical field
The present invention relates to techniques of Dyeing Wastewater Treatment fields, and in particular to a kind of side that antimony is efficiently removed from dyeing waste water Method.
Background technique
Catalyst used in the synthesis process of polyester raw material polyester about 95% or more is the chemical combination such as antimony acetate or antimony glycol Object, calculating the ratio that antimony element occupies in these catalyst according to the atomic weight of each element is about 40%.Dacron is washed Synthetic fibre blended fabric requires greatly the alkali desizing before printing and dyeing, some also need to carry out special alkali decrement treatment.And it is above-mentioned processed Journey can bring above-mentioned antimony in dyeing waste water into.Requirement of the country to water prevention and cure of pollution is increasingly strict, has promulgated that water pollution control " is spun Knit Dyeing & Finishing Industry pollution discharge standard " (GB4287-2012), and require the discharge in its standard of relevant enterprise strict implement It is required that wherein standard modification list in 2015 proposes that total antimony discharge is not higher than the control requirement of 0.1mg/l.Do not produced from chemical fibre In the case that product source solves antimony-containing catalyst use, it is exceeded that many enterprises in textile dyeing and finishing industry face antimony in discharge water Risk.
Chinese patent CN201610423772.5, the minimizing technology of antimony, date of application in a kind of dyeing waste water of patent name Disclose a kind of print being made of conditioning tank, flotation tank, hydrolytic tank, biochemistry pool, secondary settling tank and three heavy ponds on June 16th, 2016 The system that waste water removes antimony is contaminated, which is related to the multiple working procedures such as sour adjusting, air-flotation process, hydrolysis, biochemical treatment and precipitating, System in combination and the process is more complicated, and in dyeing waste water there is also a large amount of organic pollutant such as dyestuff, slurry, auxiliary agent with And the heavy metal ion such as also a small amount of copper, chromium, zinc, arsenic, complicated component, therefore practical antimony removal effect is unsatisfactory.
Summary of the invention
For there is a problem of that excessive antimony causes discharge of wastewater exceeded in dyeing waste water, the purpose of the present invention is to provide one The method of kind efficient removal antimony from dyeing waste water, can effectively remove the antimony in dyeing waste water, and can remove major part Organic pollutant, meet the discharge standard of dyeing waste water.
The present invention provides the following technical solution:
A method of efficiently removing antimony from dyeing waste water, comprising the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to acid range, Fenton reagent is then added, is stirred to react；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjusts pH value and stirred to there is floccule generation；
(4) flocculant is added into pretreatment fluid, stirs flocculation reaction；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
In the method for slave dyeing waste water removing antimony of the invention, add adjusting pH to acid after dyeing waste water is removed solid matter Property, Fenton reagent is then added, the Strong oxdiative system generated using Fenton reagent reaction is by the organic pollutant in dyeing waste water Oxidation reaction removes, and the COD concentration in dyeing waste water is greatly reduced, and antimony organic release in part is converted to inorganic antimony ion, Interference of the organic pollutant to the removing of antimony below is excluded while removing organic pollutant, then adjusts the pH of organic wastewater The ferric iron for generating Fenton's reaction is converted to ferric hydroxide precipitate and forms flocculate, thus in flocculation adsorption dyeing waste water Then the metal ions such as antimony and the lower copper of concentration, chromium, zinc and remaining organic pollutant add flocculant and strengthen hydrogen The flocculating effect of iron oxide, to improve the specificity of the removing to antimony and other heavy metal ion, the removal effect of antimony Preferably.It is then fed into air-floating apparatus and separates filter residue and aqueous, obtain efficient removal antimony, and COD concentration and other heavy metals The printing and dyeing recycle-water that ion concentration is effectively reduced.
As a preference of the present invention, the pH value of the pretreatment fluid adjusted in step (2) is 3~5, Fenton reagent used is matter The ferrous sulfate solution of 8~15wt% of concentration and the hydrogen peroxide solution of 25~40wt% are measured, hydrogen peroxide solution is first added, adds sulphur Sour ferrous iron solution, wherein hydrogen peroxide solution is 1.2~2wt ‰ with respect to the mass ratio of pretreatment fluid, ferrous sulfate and hydrogen peroxide Mass ratio is 3~8:1,30~60min of reaction time.Ferrous sulfate and hydrogen peroxide react the hydroxyl free for the strong oxidizing property to be formed Base to form Strong oxdiative atmosphere in dyeing waste water.It is ferrous excessively then to produce ferric iron as far as possible, and ferrous reproducibility is strong, Extra ferrous iron is flocculated removing by forming hydroxide precipitating in subsequent processes.
As the preferred of the method for the present invention, the range of the pH value adjusted in step (3) is 6.5~9.PH is adjusted to 6.5 ~9, to form iron hydroxide floccule, and so that the metal ions such as copper, zinc, chromium is converted into hydroxide precipitating, and by hydrogen-oxygen Change the absorption of iron flocculate.When pH is higher due to iron hydroxide floccule body surface OH-Excessively, it is unfavorable for the de- of antimony ion instead It removes.
It further include that pre- place is added after floccule generates into pretreatment fluid as the preferred of the method for the present invention, in step (3) Manage the modified wood fibre element of 1~2wt of liquid quality ‰.Lignocellulosic is organic wadding fibrous substance, the shape in dyeing waste water At three-dimensional net structure, the adhesive force of iron hydroxide floccule is mixed with iron hydroxide floccule by force, includes by absorption Heavy metal ion including antimony strengthens the flocculating effect of iron hydroxide floccule.
As the preferred of the method for the present invention, modified wood fibre element used is to obtain through following procedure: histidine is dispersed It is dissolved in MES buffer solution, histidine quality specific gravity is 1.0~2.0wt%, and MES buffer quality specific gravity is then added and is 0.3~0.7wt% polyethylene glycol condensating glycerine ether is uniformly dissolved, and buffer is heated to 50~60 DEG C, adds MES buffer Quality specific gravity is that the cellulose powder of 2~3wt% is uniformly dispersed, and ultrasonic wave added vibrates 30~60min, is then freeze-dried, and rush It is dried again after washing.Contain hydroxyl in histidine and lignocellulosic, and the glycidyl in polyethylene glycol condensating glycerine ether It can react with hydroxyl, therefore histidine is grafted to wood fibre using polyethylene glycol condensating glycerine ether as crosslinking agent The surface of element, lignocellulosic is not soluble in water and keeps wadding fibrous state, can adsorb and flocculate heavy metal ion and strengthen The flocculation ability of iron hydroxide, and histidine has amino and imidazole radicals, it is positively charged after hydrolyzing in aqueous solution, and in hydrogen-oxygen Changing i.e. preferred pH in iron acting dyeing waste water alkaline range is in 6.5~9, and antimony is mainly with Sb (OH)6-、SbO3-State is deposited , therefore ionic bond is formed between amine groups that can be positively charged with histidine and imidazole group, antimony is adsorbed onto lignin On cellulose, the absorption and flocculation ability of lignocellulose and iron hydroxide flocculate to antimony are enhanced, comparing, other are heavy Metal ion then has stronger removing specificity, improves the antimony removal efficiency of dyeing waste water.
As the preferred of the method for the present invention, step (5) further includes will be after the aqueous adjusting pH value after dissolved air flotation to 2~4 It is passed through in the adsorption tank containing rice hull carbon adsorption layer and absorbs and filter, aqueous flow velocity is 2~5BV/h.By the aqueous after flocculation separation It is adjusted to acid range, the hydroxide of remaining suspension in solution is precipitated and is converted into ionic condition with antimony, and by rice hull carbon Absorption, while remaining some organic pollutants can also be adsorbed by rice hull carbon, further purify dyeing waste water, and it is de- to improve antimony Except efficiency.
As the preferred of the method for the present invention, rice hull carbon used is made via following procedure: phenolic resin is dissolved in third In ketone, powdered rice hulls then are added and potassium oxide ultrasonic disperse is uniform, then evaporation drying, obtained solids is placed in nitrogen 800~900 DEG C are calcined 4~6 hours, and room temperature is then cooled to.Phenolic resin and potassium oxide are loaded into oxygen barrier on powdered rice hulls forge Burn, phenolic resin and rice husk form the charcoal skeleton cross-linked network of interpenetrating after firing, make to generate in rice hull carbon more hole and Point is adsorbed, is got a promotion to the small molecule organic pollutant in dyeing waste water, heavy metal ion adsorbed ability.And potassium oxide is molten It is filled in after melting in charcoal skeleton cross-linked network, is dissolved in acidic aqueous solution, make to form alkaline atmosphere inside rice hull carbon, to make The heavy metal ion of absorption is deposited in rice hull carbon, strengthens the adsorbing and removing to heavy metal ion.
As the preferred of the method for the present invention, the mass ratio of powdered rice hulls, phenolic resin and potassium oxide is 2~3:1~1.8:1.2 ~2.
As the preferred of the method for the present invention, flocculant used in step (4) is polyacrylamide, polyvinyl lactam or poly- Ethylene oxide, additional amount are 3~5wt ‰ of pretreatment fluid quality.Flocculant used be flocculant in non-ion type, strong applicability, And it is good to the flocculating effect of heavy metal ion through practice discovery, it is acted on the cooperative reinforcing of iron hydroxide floccule high.
Beneficial effects of the present invention are as follows:
Removal organic polluter is removed first using Fenton's reaction in method of the invention, then recycles the iron hydroxide and wadding of generation Solidifying agent removes the heavy metal ion such as antimony and a small amount of copper, chromium, zinc, stage by stage by organic pollutant removal and heavy metal ion Processing improves the antimony effectively removed in dyeing waste water except antimony specificity, and COD concentration and other heavy metal ion is greatly reduced Concentration.
Specific embodiment
A specific embodiment of the invention is described further below.
Unless otherwise instructed, raw material employed in the present invention is commercially available or commonly used in the art, such as Without special instruction, the method in following embodiments is the conventional method of this field.
Embodiment 1
A method of efficiently removing antimony from dyeing waste water, comprising the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to 3, Fenton reagent is then added, Fenton reagent is mass concentration 8% Ferrous sulfate solution and 25wt% hydrogen peroxide solution, hydrogen peroxide solution is first added, adds ferrous sulfate solution, sulfuric acid is sub- The mass ratio of iron and hydrogen peroxide is 6:1, and hydrogen peroxide solution is 2wt ‰ with respect to the mass ratio of pretreatment fluid, stirs sufficiently reaction 30min；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjusts pH value to 6.5 and stirred to there is floccule generation；
(4) flocculant polyethylene glycol oxide is added to pretreatment fluid, additional amount is the 3wt ‰ of pretreatment fluid quality, is stirred to react 30min；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 26 μ g/L, total antimony removing by 162 μ g/L Rate 83.9%, COD concentration are down to 57mg/L by 215mg/L, and COD removal efficiency reaches 73.5%, coloration removal efficiency 86.2%.
Embodiment 2
A method of efficiently removing antimony from dyeing waste water, comprising the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to 4, Fenton reagent is then added, Fenton reagent is mass concentration 10% Ferrous sulfate solution and 30wt% hydrogen peroxide solution, hydrogen peroxide solution is first added, adds ferrous sulfate solution, sulfuric acid is sub- The mass ratio of iron and hydrogen peroxide is 3:1, and hydrogen peroxide solution is 1.6wt ‰ with respect to the mass ratio of pretreatment fluid, is stirred to react 40min；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjusts pH value to 7 and stirred to there is floccule generation；
(4) flocculant polyacrylamide is added into pretreatment fluid, additional amount is the 4wt ‰ of pretreatment fluid quality, is stirred to react 40min；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 27 μ g/L, total antimony removing by 172 μ g/L Rate 84.3%, COD concentration are down to 52mg/L by 203mg/L, and COD removal efficiency reaches 74.4%, coloration removal efficiency 87.1%.
Embodiment 3
A method of efficiently removing antimony from dyeing waste water, comprising the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to 5, Fenton reagent is then added, Fenton reagent is mass concentration The ferrous sulfate solution of 15wt% and the hydrogen peroxide solution of 40wt%, are first added hydrogen peroxide solution, add ferrous sulfate solution, sulphur The sour ferrous mass ratio with hydrogen peroxide is 3:1, and hydrogen peroxide solution is 1.2wt ‰ with respect to the mass ratio of pretreatment fluid, is stirred to react 60min；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjust pH value and 9 stirring to there is floccule generation, then plus Enter the modified wood fibre element of pretreatment fluid quality 1wt ‰, and stirs；
(4) flocculant polyvinyl lactam is added into pretreatment fluid, additional amount is the 5wt ‰ of pretreatment fluid quality, is stirred to react 60min；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
Modified wood fibre element used in step (3) is obtained through following procedure: by histidine dispersing and dissolving in MES buffer solution In, histidine quality specific gravity is 1.0wt%, and it is 0.3wt% polyethylene glycol condensating glycerine ether that MES buffer quality specific gravity, which is then added, It is uniformly dissolved, buffer is heated to 50 DEG C, it is equal to add the cellulose powder dispersion that MES buffer quality specific gravity is 2wt% Even, ultrasonic wave added vibrates 30min, is then freeze-dried, and dries again after rinsing.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 19 μ g/L, total antimony removing by 178 μ g/L Rate 89.3%, COD concentration are down to 50mg/L by 224mg/L, and COD removal efficiency reaches 77.7%, coloration removal efficiency 89.2%.
Embodiment 4
A method of efficiently removing antimony from dyeing waste water, comprising the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to 4, Fenton reagent is then added, Fenton reagent is mass concentration The ferrous sulfate solution of 10wt% and the hydrogen peroxide solution of 30wt%, are first added hydrogen peroxide solution, add ferrous sulfate solution, sulphur The sour ferrous mass ratio with hydrogen peroxide is 6:1, and hydrogen peroxide solution is 1.8wt ‰ with respect to the mass ratio of pretreatment fluid, is stirred to react 50min；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjust pH value and 7 stirring to there is floccule generation, then plus Enter the modified wood fibre element of the 1.5wt ‰ of pretreatment fluid quality, and stirs；
(4) flocculant polyacrylamide is added to pretreatment fluid, additional amount is the 4wt ‰ of pretreatment fluid quality, is stirred to react 40min；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
Wherein, modified wood fibre element used in step (3) is obtained through following procedure: histidine dispersing and dissolving is delayed in MES It rushes in solution, histidine quality specific gravity is 1.6wt%, MES buffer quality specific gravity is added then as the condensation of 0.5wt% polyethylene glycol Glycerin ether is uniformly dissolved, and buffer is heated to 55 DEG C, adds the cellulose powder that MES buffer quality specific gravity is 2.5wt% It is uniformly dispersed, ultrasonic wave added vibrates 40min, is then freeze-dried, and dry again after rinsing.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 15 μ g/L, total antimony removing by 180 μ g/L Rate 91.6%, COD concentration are down to 42mg/L by 225mg/L, and COD removal efficiency reaches 81.3%, coloration removal efficiency 91.2%.
Embodiment 5
A method of from dyeing waste water efficiently remove antimony, with embodiment 4 the difference is that:
Modified wood fibre element used in step (3) is obtained through following procedure: by histidine dispersing and dissolving in MES buffer solution, Histidine quality specific gravity is 2.0wt%, and it is that 0.7wt% polyethylene glycol condensating glycerine ether is molten that MES buffer quality specific gravity, which is then added, Buffer uniformly, is heated to 60 DEG C by solution, is added the cellulose powder that MES buffer quality specific gravity is 3wt% and is uniformly dispersed, Ultrasonic wave added vibrates 60min, is then freeze-dried, and dries again after rinsing.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 21 μ g/L, total antimony removing by 169 μ g/L Rate 87.6%, COD concentration are down to 45mg/L by 210mg/L, and COD removal efficiency reaches 78.6%, coloration removal efficiency 90.2%.
Embodiment 6
A method of from dyeing waste water efficiently remove antimony, with embodiment 4 the difference is that,
In step (5), pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, adjusts the pH value of aqueous to being passed through after 4 It is absorbed and filter in adsorption tank containing rice hull carbon adsorption layer, aqueous flow velocity is 2BV/h, obtains the printing and dyeing recycle-water of removing antimony.
Rice hull carbon is made via following procedure: in acetone by phenolic resin dissolution, powdered rice hulls and potassium oxide is then added Ultrasonic disperse is uniform, then evaporation drying, and obtained solids is placed in nitrogen and is calcined 6 hours for 800 DEG C, room is then cooled to Temperature, the mass ratio of powdered rice hulls, phenolic resin and potassium oxide are 2:1:2.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 14 μ g/L, total antimony removing by 175 μ g/L Rate 92.0%, COD concentration are down to 41mg/L by 226mg/L, and COD removal efficiency reaches 81.8%, coloration removal efficiency 90.8%.
Embodiment 7
A method of from dyeing waste water efficiently remove antimony, with embodiment 4 the difference is that,
In step (5), pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, adjusts the pH value of aqueous to being passed through after 3 It is absorbed and filter in adsorption tank containing rice hull carbon adsorption layer, aqueous flow velocity is 4BV/h, obtains the printing and dyeing recycle-water of removing antimony.
Rice hull carbon is made via following procedure: in acetone by phenolic resin dissolution, powdered rice hulls and potassium oxide is then added Ultrasonic disperse is uniform, then evaporation drying, and obtained solids is placed in nitrogen and is calcined 5 hours for 850 DEG C, room is then cooled to Temperature, the mass ratio of powdered rice hulls, phenolic resin and potassium oxide are 3:1.5:1.6.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 12 μ g/L, total antimony removing by 183 μ g/L Rate 93.4%, COD concentration are down to 37mg/L by 207mg/L, and COD removal efficiency reaches 82.1%, coloration removal efficiency 91.8%.
Embodiment 8
A method of from dyeing waste water efficiently remove antimony, with embodiment 4 the difference is that,
In step (5), pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, adjusts the pH value of aqueous to being passed through after 2 It is absorbed and filter in adsorption tank containing rice hull carbon adsorption layer, aqueous flow velocity is 5BV/h, obtains the printing and dyeing recycle-water of removing antimony.
Rice hull carbon used is made through following procedure: in acetone by phenolic resin dissolution, powdered rice hulls and oxygen is then added It is uniform to change potassium ultrasonic disperse, then evaporation drying, obtained solids is placed in nitrogen and is calcined 4 hours for 900 DEG C, is then cooled down To room temperature, the mass ratio of powdered rice hulls, phenolic resin and potassium oxide is 3:1:2.
The dyeing waste water pretreatment fluid handled by the above method, total antimony concentration are down to 14 μ g/L, total antimony removing by 179 μ g/L Rate 92.1%, COD concentration are down to 41mg/L by 225mg/L, and COD removal efficiency reaches 81.8%, coloration removal efficiency 90.9%.

Claims (9)

1. a kind of method for efficiently removing antimony from dyeing waste water, which comprises the following steps:
(1) dyeing waste water is pre-processed, the solid matter of filtering and removing indissoluble obtains pretreatment fluid；
(2) acid solution is added into pretreatment fluid and adjusts pH value to acid range, Fenton reagent is then added, is stirred to react；
(3) lye is added in the pretreatment fluid sufficiently reacted, adjusts pH value and stirred to there is floccule generation；
(4) flocculant is added into pretreatment fluid, stirs flocculation reaction；
(5) then pretreatment fluid is sent into air-floating apparatus and separates dross and aqueous, obtain the printing and dyeing recycle-water of removing antimony.
2. the method according to claim 1 for efficiently removing antimony from dyeing waste water, which is characterized in that adjusted in step (2) Pretreatment fluid pH value be 3~5, Fenton reagent used be 8~15wt% of mass concentration ferrous sulfate solution and 25~ The hydrogen peroxide solution of 40wt%, is first added hydrogen peroxide solution, adds ferrous sulfate solution, and wherein hydrogen peroxide solution is located in advance relatively The mass ratio of liquid is managed as 1.2~2wt ‰, the mass ratio of ferrous sulfate and hydrogen peroxide is 3~8:1,30~60min of reaction time.
3. the method according to claim 2 for efficiently removing antimony from dyeing waste water, which is characterized in that adjusted in step (3) PH value range be 6.5~9.
4. the method according to claim 1 or 2 or 3 for efficiently removing antimony from dyeing waste water, which is characterized in that step (3) In further include floccule generation after into pretreatment fluid be added 1~2wt of pretreatment fluid quality ‰ modified wood fibre element.
5. the method according to claim 4 for efficiently removing antimony from dyeing waste water, which is characterized in that the wooden fibre of modification used Dimension element is obtained through following procedure: by histidine dispersing and dissolving in MES buffer solution, histidine quality specific gravity be 1.0~ 2.0wt%, it is that 0.3~0.7wt% polyethylene glycol condensating glycerine ether is uniformly dissolved that MES buffer quality specific gravity, which is then added, will be delayed Fliud flushing is heated to 50~60 DEG C, adds the cellulose powder that MES buffer quality specific gravity is 2~3wt% and is uniformly dispersed, ultrasound 30~60min of auxiliary oscillating, is then freeze-dried, and dries again after rinsing.
6. the method according to claim 4 for efficiently removing antimony from dyeing waste water, which is characterized in that step (5) further includes It is absorbed and filter being passed through in the adsorption tank containing rice hull carbon adsorption layer after the aqueous adjusting pH value after dissolved air flotation to 2~4, aqueous Flow velocity is 2~5BV/h.
7. the method according to claim 6 for efficiently removing antimony from dyeing waste water, which is characterized in that rice hull carbon warp used Following procedure is made: in acetone by phenolic resin dissolution, powdered rice hulls then is added and potassium oxide ultrasonic disperse is uniform, then steam It is dry dry, obtained solids is placed in nitrogen and is calcined 4~6 hours for 800~900 DEG C, room temperature is then cooled to.
8. the method according to claim 7 for efficiently removing antimony from dyeing waste water, which is characterized in that powdered rice hulls, phenolic aldehyde tree The mass ratio of rouge and potassium oxide is 2~3:1~1.8:1.2~2.
9. the method according to claim 1 or 2 or 3 for efficiently removing antimony from dyeing waste water, which is characterized in that step (4) In flocculant used be polyacrylamide, polyvinyl lactam or polyethylene glycol oxide, additional amount be pretreatment fluid quality 3~ 5wt‰。
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