CN102206001A - Composite decolorizer as well as preparation method and application thereof - Google Patents
Composite decolorizer as well as preparation method and application thereof Download PDFInfo
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- CN102206001A CN102206001A CN201110109703.4A CN201110109703A CN102206001A CN 102206001 A CN102206001 A CN 102206001A CN 201110109703 A CN201110109703 A CN 201110109703A CN 102206001 A CN102206001 A CN 102206001A
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- calcium peroxide
- polyacrylamide
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Abstract
The invention belongs to the technical field of chemical engineering, in particular relates to a solid composite decolorizer as well as a preparation method and application thereof. The composite decolorizer consists of ferrous sulfate heptahydrate, polymerized ferric sulfate, calcium peroxide and polyacrylamide. The preparation method comprises the following steps: directly mixing ferrous sulfate heptahydrate solid and polymerized ferric sulfate solid with calcium peroxide solid at room temperature, and smashing; and then mixing the mixture with instant anionic polyacrylamide ultrafine powder, so as to obtain the solid composite decolorizer product. The composite decolorizer has a redox property and simultaneously has a comprehensive coagulation property of iron salt and polyacrylamide; and the composite decolorizer has the advantages of simple preparation method, available raw materials, low cost, good treatment effect and wide development value and application prospect, and is suitable for rapid treatment of dye wastewater such as printing and dyeing wastewater.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of compound discoloring agent, preparation method and application thereof.
Background technology
The textile printing and dyeing dyeing waste-water, because its water yield is big, the colourity height, complicated component, contain dyestuff, slurry, auxiliary agent, acid, alkali, fiber impurity and inorganic salt etc. in the waste water, heavy metal elements such as amino-complex and copper, chromium, zinc, arsenic have bigger toxicity in the dye structure.10～20% dyestuff enters in the waste water serious environment pollution in the dyeing course of processing at present.Along with the development of dyestuffs industries and the progress of printing and dyeing processing technology, the stability of dye structure greatly improves, and handling to decolouring has increased difficulty, and the decolorization of dyeing problem has become a great problem of being badly in need of solution in the domestic and international wastewater treatment at present.
The method that present many printing and dyeing mills adopt chemical treatment to combine with biochemical treatment, microbial method degradation of dye molecule and organism are adopted in biochemical treatment, but harmful molecule degradation rate is low in the biochemical treatment process, facility investment is big, therefore the working cost height selects the effective treatment process of a kind of simple economy to become the research emphasis of decolorizing printing and dyeing waste water.Except that biochemical process, other physical chemistry or chemical decolorization such as absorption method, oxidation reduction process, ion exchange method, embrane method, Coagulation Method etc. the report of big quantity research and application is all arranged, but treatment effect are not very good.
Chemical coagulator can be divided into inorganic and organic two big classes.At present the inorganic coagulant that occurs comprises metallic salt and inorganic polymer polyelectrolyte, wherein based on the compound of molysite, magnesium salts, aluminium salt and silicon, calcium constituent.According to applicable cases, all the percent of decolourization to some water-soluble dye wastewaters is not high for simple aluminium salt such as aluminium chlorohydroxide, Tai-Ace S 150, trivalent iron salt, and the pH scope of using is narrower.Ferrous sulfate all has decolorizing effect preferably for most of water-soluble dye, for example handles the sulfuration dyeing waste-water, and chroma removal rate is 95%, and sulfide and BOD clearance are 96% and 59%.But because the mechanism of ferrous sulfate decolouring is with the chromophore reduction, reduzate is that organic molecule can not be removed by effective coagulation, so the clearance of CODcr is not high, and bigger to the consumption of basicity in the solution, and the consumption of coagulating agent is also bigger.
A large amount of research and application practices show, adopt inorganic coagulant to comprise that molysite, aluminium salt, magnesium salts and inorganic flocculating agent have good decolorizing effect to the dyestuff that is present in the waste water with colloid or suspended state, as the vat dyes after dispersed dye, thioxine dyes, the oxidation, bigger substantive dyestuff and the neutral dye of glacial dye, pigment and molecular weight after the coupling; Then coagulate decoloring effect is undesirable to the water-soluble dye that be difficult for to form colloidal particle such as the micromolecular substantive dyestuff waste water of matching stain, reactive dyestuffs and part.
Chinese patent (application number: 95101739) provide a kind of novel method that is suitable for the Dyhard RU 100 formaldehyde condensation products preparation that decoloring dye waste water uses, i.e. " two step method condensation " technology, make technological process comparatively stable, be easy to control, and the optimization by material choice and processing condition, make the Dyhard RU 100 formaldehyde of preparation have the effect of broad-spectrum high efficacy.But above-mentioned two kinds of methods all adopt formaldehyde as main raw material, because residual formaldehyde has potential harm for the water body biology.Simultaneously above-mentioned synthesis technique forms the oligopolymer of a large amount of amine, if when therefore dosage is bigger, the COD effect of removing in the water body is bad, raises on the contrary sometimes.
The conjugated system or the chromophoric group that destroy dyestuff by redoxomorphism are the effective ways that the printing and dyeing decolouring is handled.Except that the oxychlorination method of routine, research emphasis mainly concentrates on ozone oxidation, hydrogen peroxide oxidation, electrolytic oxidation and photoxidation aspect both at home and abroad.Ozone is good decolouring oxygenant, for contain water-soluble dye waste water as active, directly, dyestuffs such as positively charged ion and acidity, its percent of decolourization is very high; Dispersed dye also there is better decolorizing effect; But other are present in reduction, sulfuration and coating in the waste water with suspended state, and decolorizing effect is relatively poor.Ozone oxidation also can combine application with other treatment technologies.As use FeSO
4, Fe
2(SO
4)
3And FeCl
3Can improve decolorizing effect with ozonize again after the cohesion; Ozone-electrolysis treatment can directly make the percent of decolourization of matching stain increase by 25 ~ 40% than simple ozonize, and alkalescence and reactive dyestuffs are increased 10%(Takahashi Nobuyuki et al. kogyo Yousi. 1982, (285): 10-16.).Ozone adds uv-radiation or carries out ionizing rays simultaneously and also can improve oxidation efficiency.Because ozone oxidation is to dye species wide adaptability, decolorizing efficiency height, O simultaneously
3Reduzate in waste water and superfluous O
3Can in solution and air, be decomposed into O rapidly
2, can not cause secondary pollution to environment.So O
3Decolouring technology has certain industrial applications prospect.The main drawback of ozone oxidation is that working cost is higher relatively at present.
Fenton reagent is liquid hydrogen peroxide and FeSO
4A kind of strong oxidation medicament that mixes by a certain percentage.Fenton reagent except that having oxygenizement, also have coagulation concurrently, so decolorizing efficiency is higher in handling the waste water process.Obtained increasingly extensive application in recent years in the decolouring of dye well waste water is handled, traditional liquid hydrogen peroxide oxidation all occurs with the form of Fenton reagent at present.In actual application, generally can select for use mineral acid to regulate wastewater pH is 2 ~ 5, adds and uses H
2O
2/ Fe
2+Handle, after with the Fenton agent treated, for further bringing into play Fe
3+Coagulation also can be adjusted the pH value again and add a small amount of polymer coagulant aids (Yamada kenji et al. Japan, kokai 29 44352.).
The Fenton oxidation technology all is with liquid hydrogen peroxide and ferrous sulfate at present, necessary in use multi-point adding, and also all inconvenient in liquid storage and the use.Therefore if use with the form of single medicament then in transportation, store and use in bring very big advantage.
Summary of the invention
The object of the invention is to provide a kind of compound discoloring agent, preparation method and application thereof, and it not only has the good decolorizing effect for waste water from dyestuff, has also that the preparation method is simple, cost is low, good stability, is convenient to characteristics such as transportation and storage.
For achieving the above object, the compound discoloring agent that the present invention proposes is made up of ferrous sulfate (containing seven crystal water), bodied ferric sulfate, calcium peroxide and instant type anionic polyacrylamide.The total iron content of product is 13～19%, and the mass percent of each active principle is:
Ferrous sulfate (seven crystal water): 35%～45%
Bodied ferric sulfate: 30%～45%
Polyacrylamide: 0.1%～0.5%
All the other are calcium peroxide, and its total mass satisfies 100%.
Among the present invention, described ferrous sulfate, bodied ferric sulfate, calcium peroxide and polyacrylamide are uniform ultrafine powder.
The used iron vitriol of the present invention is commercially available industrial goods body.Ferrous sulfate is a kind of discoloring agent and coagulating agent, has certain decolouring and coagulation.
The used solid ferric polysulfate of the present invention is commercially available solid phase prod, is a kind of coagulating agent, has good coagulation.
The used calcium peroxide of the present invention is commercially available solid phase prod, is a kind of coagulating agent, oxygenant, has good coagulation and oxygenizement.
The used instantly-soluble anion pp acid ammonium of the present invention is commercially available solid phase prod, is a kind of flocculation agent, has good throwing out.
The preparation method of the compound discoloring agent that the present invention proposes, concrete steps are:
(1) at ambient temperature, iron vitriol, bodied ferric sulfate and calcium peroxide are mixed in proportion, utilize ball mill to be crushed to 150 orders;
(2) in the solid that mixes, add instant type anionic polyacrylamide ultrafine powder, and then mix, obtain the compound discoloring agent of solid.
With iron vitriol and bodied ferric sulfate, directly mix among the present invention, utilize the very slow characteristics of speed of response between the solid, obtain solid ferric polysulfate, the solid mixture of ferrous sulfate and calcium peroxide, promptly inorganic discoloring agent with calcium peroxide.According to the characteristic that will handle dyestuff or dyeing and printing sewage, the ratio of above-mentioned substance can suitably be adjusted.
The compound discoloring agent that utilizes the present invention to prepare is suitable for handling the dyeing waste water that the pH value is 5～12 scopes.
Discoloring agent of the present invention also can be used with other types such as inorganic coagulant (for example polymerize aluminum chloride, polyaluminium sulfate, Tai-Ace S 150, aluminium iron polychloride) or organic floculant (for example various polyacrylamides, polyamine, diallyldimethylammonium chloride homopolymer and multipolymer etc.), can improve flco particle diameter and flocculation rate, but coagulant aids should add discoloring agent reaction later stage use.
Among the present invention, the particle diameter of described solid decolorizer is less than 150 orders.
The compound discoloring agent of the present invention's preparation is generally controlled the content of calcium peroxide 25～35%.In the process of water treatment, when molysite can dissolve fast, simultaneously with calcium peroxide generation catalytic oxidation, reach the purpose of quick degraded solvability dyestuff, can in 5～10min, can dissolve fully owing to instant type anionic polyacrylamide simultaneously, more form the extended pattern molecular solution thereby form, thereby in absorption and bridge formation flocculation process, can greater advantages bring into play macromolecular flocculating effect.Redox, coagulation and flocculation process can be implemented by the composite decoloring agent single step reaction like this, be reached the purpose of removing colourity and other pollutents, especially even more ideal for the lower dyeing waste water effect of suspended matter.And the flco that conventional poly aluminium chloride and polyiron sulfate often form is light, be not easy precipitation, and the characteristic of this compound discoloring agent can remedy the deficiency of poly aluminium chloride and polyiron sulfate fully.
The present invention adopts single stage method to prepare the compound discoloring agent of solid, and it is simple to have the preparation method, and raw material is easy to get, and cost is low, and high treating effect has wide development value and application prospect.
Embodiment
The characteristics that the invention is further illustrated by the following examples, but these embodiment are used for limiting the scope of the invention by any way.
The application processing method of the compound discoloring agent of the present invention is: this discoloring agent is directly used with solid form, utilize the screw rod gauge, the metering back adds desires in the treating water.Stir, reacted 10-20 minute, have a large amount of flosss to generate, separate, do not have specific requirement for water processing establishment with settling process.The throw out treatment process is identical with the method for conventional processing mud.
In the following examples and the Comparative Examples, the colourity of the waste water from dyestuff of configuration all adopts " measuring method of State Standard of the People's Republic of China's water quality colourity " (GB11903-89) with the colourity testing method that adds after product of the present invention decolours, be directed to trade effluent, so adopt the extension rate method, the percent of decolourization method of calculation as shown in the formula:
The preparation of embodiment 1 compound discoloring agent
To contain 30.0 kg iron vitriols, 28.0 kg particulate state bodied ferric sulfates (ferric iron content is 20.2%, basicity 12.1%) join in the ball mill with the block calcium peroxide of 20.0 kg, and being crushed to particle diameter is 150 orders.Carry out uniform mixing with the instant type anionic polyacrylamide of 0.3kg (molecular weight 1000-1500 ten thousand, negatively charged ion degree 30%, commercially available prod) then, promptly obtain compound discoloring agent.The shared ratio of each component sees Table 1, and experimental result sees Table 2.
The preparation of embodiment 2 compound discoloring agents
To contain 30.0 kg iron vitriols, 24.0 kg particulate state bodied ferric sulfates (ferric iron content is 20.2%, basicity 12.1%) join in the ball mill with the block calcium peroxide of 24.0 kg, and being crushed to particle diameter is 150 orders.Carry out uniform mixing with the instant type anionic polyacrylamide of 0.3kg (molecular weight 1000-1500 ten thousand, negatively charged ion degree 30%, commercially available prod) then, promptly obtain compound discoloring agent.The shared ratio of each component sees Table 1, and experimental result sees Table 2.
The preparation of embodiment 3 compound discoloring agents
To contain 34.0 kg iron vitriols, 28.0 kg particulate state bodied ferric sulfates (ferric iron content is 20.2%, basicity 12.1%) join in the ball mill with the block calcium peroxide of 24.0 kg, and being crushed to particle diameter is 150 orders.Carry out uniform mixing with the instant type anionic polyacrylamide of 0.4kg (molecular weight 1000-1500 ten thousand, negatively charged ion degree 30%, commercially available prod) then, promptly obtain compound discoloring agent.The shared ratio of each component sees Table 1, and experimental result sees Table 2.
The preparation of embodiment 4 compound discoloring agents
To contain 30.0 kg iron vitriols, 26.0 kg particulate state bodied ferric sulfates (ferric iron content is 20.2%, basicity 12.1%) join in the ball mill with the block calcium peroxide of 26.0 kg, and being crushed to particle diameter is 150 orders.Carry out uniform mixing with the instant type anionic polyacrylamide of 0.2kg (molecular weight 1000-1500 ten thousand, negatively charged ion degree 30%, commercially available prod) then, promptly obtain compound discoloring agent.The shared ratio of each component sees Table 1, and experimental result sees Table 2.
The preparation of embodiment 5 compound discoloring agents
To contain 30.0 kg iron vitriols, 30.0 kg particulate state bodied ferric sulfates (ferric iron content is 20.2%, basicity 12.1%) join in the ball mill with the block calcium peroxide of 26.0 kg, and being crushed to particle diameter is 150 orders.Carry out uniform mixing with the instant type anionic polyacrylamide of 0.2kg (molecular weight 1000-1500 ten thousand, negatively charged ion degree 30%, commercially available prod) then, promptly obtain compound discoloring agent.The shared ratio of each component sees Table 1, and experimental result sees Table 2.
Comparative Examples 1
50.0 kg iron vitriols (containing seven crystal water) are joined in the ball mill, and being crushed to particle diameter is 150 orders, obtains the Comparative Examples product.Experimental result sees Table 2.
Comparative Examples 2
50.0 kg solid ferric polysulfates are joined in the ball mill, and being crushed to particle diameter is 150 orders, obtains the Comparative Examples product.Experimental result sees Table 2.
Comparative Examples 3
50.0 kg solid peroxygen calcium are joined in the ball mill, and being crushed to particle diameter is 150 orders, obtains the Comparative Examples product.Experimental result sees Table 2.
Comparative Examples 4
The instant type anionic polyacrylamide of 5.0 kg is joined in the ball mill, and being crushed to particle diameter is 150 orders, obtains the Comparative Examples product.Experimental result sees Table 2.
The prepared compound discoloring agent effective constituent of table 1 the present invention is formed
Table 2 experimental result
Claims (5)
1. a compound discoloring agent is characterized in that being made up of ferrous sulfate (containing seven crystal water), bodied ferric sulfate, calcium peroxide and instant type anionic polyacrylamide, and the total iron content of product is 13～19%, and the mass percent of each active principle is:
Ferrous sulfate (seven crystal water): 35%～45%
Bodied ferric sulfate: 30%～45%
Polyacrylamide: 0.1%～0.5%
All the other are calcium peroxide, and its total mass satisfies 100%.
2. the preparation method of a compound discoloring agent as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) at ambient temperature, iron vitriol, bodied ferric sulfate and calcium peroxide are mixed in proportion, utilize ball mill to be crushed to 150 orders;
(2) in the solid that mixes, add instant type anionic polyacrylamide ultrafine powder, and then mix, obtain the compound discoloring agent of solid.
3. the application of compound discoloring agent as claimed in claim 1 in handling the dyeing waste water that the pH value is 5～12 scopes.
4. compound discoloring agent according to claim 1, the particle diameter that it is characterized in that compound back solid decolorizer is less than 150 orders.
5. preparation method according to claim 2 is characterized in that described ferrous sulfate, bodied ferric sulfate, calcium peroxide and polyacrylamide are uniform ultrafine powder.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864187A (en) * | 2012-12-09 | 2014-06-18 | 曹健 | Method for preparing polyphosphate aluminum ferric sulfate as flocculant |
| CN107162135A (en) * | 2017-05-27 | 2017-09-15 | 广东睿洁环保工程有限公司 | A kind of fast purification agent of cities and towns black and odorous water |
| CN109354253A (en) * | 2018-11-28 | 2019-02-19 | 同济大学 | Method that is a kind of while removing pumping plant useless Organic substance in water and phosphorus |
| CN113548725A (en) * | 2021-08-05 | 2021-10-26 | 上海大学 | Composite decoloring agent, preparation method and application thereof |
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| CN101402481A (en) * | 2008-10-16 | 2009-04-08 | 同济大学 | Mesoporous adsorption type aluminum salt composite flocculent synthesis method and uses thereof |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101223109A (en) * | 2005-07-14 | 2008-07-16 | 出光兴产株式会社 | Method for treating water containing hardly decomposable substance |
| CN101402481A (en) * | 2008-10-16 | 2009-04-08 | 同济大学 | Mesoporous adsorption type aluminum salt composite flocculent synthesis method and uses thereof |
Non-Patent Citations (2)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864187A (en) * | 2012-12-09 | 2014-06-18 | 曹健 | Method for preparing polyphosphate aluminum ferric sulfate as flocculant |
| CN107162135A (en) * | 2017-05-27 | 2017-09-15 | 广东睿洁环保工程有限公司 | A kind of fast purification agent of cities and towns black and odorous water |
| CN109354253A (en) * | 2018-11-28 | 2019-02-19 | 同济大学 | Method that is a kind of while removing pumping plant useless Organic substance in water and phosphorus |
| CN113548725A (en) * | 2021-08-05 | 2021-10-26 | 上海大学 | Composite decoloring agent, preparation method and application thereof |
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Application publication date: 20111005 |