CN105585099A - Decolorization treatment method for colored liquid waste - Google Patents
Decolorization treatment method for colored liquid waste Download PDFInfo
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- CN105585099A CN105585099A CN201510977594.6A CN201510977594A CN105585099A CN 105585099 A CN105585099 A CN 105585099A CN 201510977594 A CN201510977594 A CN 201510977594A CN 105585099 A CN105585099 A CN 105585099A
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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Abstract
The invention discloses a decolorization treatment method for colored liquid waste. A loaded metal catalyst and a reducing agent are adopted, colored liquid waste can be rapidly decolored, no loaded metal catalyst is consumed in the decolorization process, and continuous colored liquid waste decolorization treatment can be maintained just by adding the reducing agent. After the loaded metal catalyst is inactivated, organic solvent or water can be adopted to conduct washing to remove pollutants attached to the surface of the catalyst, the loaded metal catalyst can have activity again, and the color of the colored liquid waste is removed rapidly together with the reducing agent. The decolorization treatment method for the colored liquid waste is simple in process, all raw materials are low in price, the quantity of treated colored liquid waste is large, large-scale application is achieved easily, the loaded metal catalyst can be cycled for a long time, and decolorization treatment of colored liquid waste is greatly lowered.
Description
Technical field
The present invention relates to a kind of decoloration treatment method of coloured waste liquid, be specifically related to one and utilize the derivative modified carrier framework material load of catechol metallic catalyst, and then the method for the coloured waste liquid decolouring of catalysis processing.
Background technology
Coloured waste liquid is one of key industry of industrial pollution control and water saving, coloured waste liquid is mainly produced by textile printing and dyeing and other industry, wherein, the coloured discharging of waste liquid amount of dyeing textile industry accounts for industry discharging of waste liquid amount more than 80%, it is the key link of impact and the development of restriction related industries, therefore, the focus that is treated as current research of coloured waste liquid. Because coloured waste liquid has that the water yield is large, content of organics is high, the feature such as complicated component and bio-refractory, conventional treatment technology mainly contains the methods such as absorption method, membrane separation process, electrochemical process, advanced oxidation processes and microorganism treatment. And these methods all exist various problems, for absorption method, topmost problem is that adsorbent reactivation is poor and adsorbance is little; There is membrane pollution problem and cost costliness in membrane separation technique; Mainly there is the problem that cost is high in electrochemical process and advanced oxidation processes; Bioanalysis existence and stability is poor, the problem that the reaction time is long.
Patent CN103521192A(Taizhou University) by after Rhizopus oryzae thalline and mixed molysite solution reaction, add cane shoots leaves powder and curing agent to prepare magnetic biological adsorption agent, but due to the restriction of adsorbent nature, can only adsorb anionic azo dyes, and there is the saturated problem of absorption in adsorbent itself, this will limit its application greatly. Patent CN1827535A(SanDa film Science Co., Ltd) by ultrafiltration circulation and nanofiltration circulation technology are combined, after again nanofiltration dislysate being processed by charcoal absorption, reach national secondary discharge standard, but the method needs loaded down with trivial details pretreatment process techniques such as () waste water adjusting, flocculating setting and clarifications, and membrane technology itself exists film to pollute and the problem of cost costliness. Patent CN101863524A(University Of Suzhou) a kind of method of photocatalytic oxidation degradation waste water containing dye is provided, the Pt nanowires that is less than 3nm by diameter is as catalyst, under illumination condition, react, catalytic reaction can complete in 20-480 minute, but nano material does not have support materials, consumption is large, and is difficult for disperseing at water body, cause rendezvous problem, this its catalytic activity of largely degrading. In addition, add diameter to be less than the Pt nanowires of 3nm in waste water from dyestuff, after the complete dyestuff of catalytic degradation, the Pt nanowires that diameter is less than 3nm is difficult to reclaim, and then can cause secondary pollution to water body, also causes the waste of Pt nanowires catalyst simultaneously.
This patent has been set forth the catalyst of working load, for the decolouring processing of coloured waste liquid. By nanocatalyst is loaded on to substrate surface, increase the surface area of catalyst, reduce the absolute dosage of catalyst, and be convenient to recycle and reuse supported catalyst for the processing of decolouring, also reduce the risk that catalyst itself pollutes water body simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of application of above-mentioned carrier to load metal catalyst. This catalyst can be applied under the effect of reducing agent as effective catalyst but be not limited to coloured liquid waste processing of the industries such as pharmacy, papermaking, printing and dyeing, pottery, leather or chemical industry.
About the preparation method (a kind of preparation method of metallic catalyst of load) of catalyst therewith patent apply for simultaneously, briefly introduce as follows: by catechol analog derivative and metal salt solution and described carrier framework material blend in the aqueous solution, stir after 10 minutes-10 hours, collect dry obtaining by centrifugal or filtration.
The invention provides following technical scheme:
A decoloration treatment method for coloured waste liquid, is characterized in that,
(a) by metallic catalyst and reducing agent for the processing of decolouring fast of coloured waste liquid, required bleaching time is 10 seconds-1 hour, the optimization time is 1 minute-10 minutes;
(b) for the decolouring processing of coloured waste liquid, metallic catalyst and reducing agent (can not limit sequentially) and are distributed in coloured waste liquid the processing of decolouring simultaneously or successively; Also metallic catalyst can be dressed up to packed column or be fixed on packed bed, dye solution and reducing agent mixed liquor are flowed through to metallic catalyst simultaneously and decoloured;
(c) for the decolouring processing of coloured waste liquid, dyestuff mass ratio 0.001 ~ 1000 in reducing agent and coloured waste liquid, is preferably 0.1 ~ 10;
(d) for the decolouring processing of coloured waste liquid, metallic catalyst lasting use capable of circulation, once adds; continue to keep active; only need to supplement reducing agent and continue for a long time to process more coloured waste liquid, the decolorizing effect of coloured waste liquid is greater than to 80%, can realize decolorizing effect and be greater than 95%;
(e) for the decolouring processing of coloured waste liquid, increase dosage or the consumption of metallic catalyst and reducing agent, can accelerate decoloring reaction, shorten decolouring required time;
(f) coloured waste liquid dye solution can be the aqueous solution and also can be the mixed solution of organic solvent or organic solvent and water, and selected reducing agent need be dissolved in coloured waste liquid;
Wherein, the metallic catalyst of processing for colorful wastewater decolouring, is characterised in that, comprises (a) catalyst backbone carrier material, the polymer coating that (b) catalyst backbone surfaces of carrier materials contains catechol derivatives; (c) play metal or metal oxide or the metal ion of catalytic action, by embedding or boning or be chelated to the polymer coating of catechol derivatives, and then be fixed to catalyst backbone surfaces of carrier materials. Wherein load on the metal of skeleton carrier material surface or metal oxide or metal ion and play catalyst action, for the decolouring processing of colorful wastewater.
Wherein, the metallic catalyst of processing for colorful wastewater decolouring, the quality percentage composition that carrier framework material accounts for described metal catalyst system is 10-99%, is preferably 75%-95%; Metallic catalyst account for described catalyst system quality percentage composition be 0.1-50.0%, be preferably 1%-20%; The quality percentage composition that described catechol derivative polymer coating accounts for described catalyst system is 0.01-50%, is preferably 0.1-10%.
Wherein, catalyst backbone carrier material is selected from and has compared with the particle powder of the inorganic material of bigger serface or Inorganic Non-metallic Materials or organic material or sheet material or sheet material. wherein inorganic material or Inorganic Non-metallic Materials include but not limited to the (imvite of clay class, tired de-soil, diatomite, bentonite, attapulgite, kaolin, atlapulgite, zeolite, illite, galapectite, vermiculite, serpentine etc.), sandstone class (river sand, sea sand, metal sand, sand after natural sandstone efflorescence etc.), stone flour class (medical stone powder, dicalcium powder, talcum powder, dolomite dust, powder of lacquer putty for use on etc.), flyash, flue dust, metal and oxide thereof or hydroxide (aluminium salt, molysite, magnesium salts, silicon salt, titanium salt and complex salt etc. thereof, conventional have alum, aluminium polychloride, PAFC, poly-ferric chloride, polymer phosphate aluminium, polymer aluminium silicate, polymeric aluminium ferrum silicate, calcium aluminate, manganese oxide, iron oxide, aluminium oxide, zirconia, antimony oxide, calcium carbonate, zinc oxide, magnesium hydroxide) etc. one or more.
Wherein, organic material includes but not limited to starch and starch Deformation Products, active carbon, Graphene and Graphene derivative, CNT and derivative thereof, polymer microsphere and powder or diaphragm (as polyethylene, polypropylene, polysulfones, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylamide, polyaniline, polystyrene, cellulose and derivative thereof).
Wherein, catechol analog derivative, is characterised in that described catechol analog derivative is a kind of organic molecule that contains dihydroxy benzenes base section and derivative thereof, and its general molecular formula is:
Its general molecular formula is:
Include but not limited to following molecular formula:
Wherein R1, R2, R3, R4, R5 is identical or different, be selected from independently of one another hydrogen, saturated and undersaturated, straight chain and side chain, replacement and unsubstituted C1-10 alkyl, and contain amino, carboxyl, sulfydryl, one or more substituents in halogen, oh group, low-grade alkyl group, lower alkoxy groups, monocyclic aryl, lower acyl group and their combination; Including, but not limited to DOPA (DOPA), dopamine and salt, 3 thereof, 4-dihydroxy benzenes methylamine, 3,4-4-dihydroxy benzaldehyde, 3,4-dihydroxy benzenes acetaldehyde, PCA or DOPAC.
Wherein, metal or metal oxide or metal ion include but not limited to copper, silver, titanium, platinum, gold etc.
Wherein, reducing agent, includes but not limited to sodium borohydride, hydrazine hydrate, ascorbic acid, polyalcohol, formaldehyde and formic acid etc.
Wherein, metallic catalyst, can fill packed column or be fixed to packed bed for colorful wastewater decolouring processing after granulation.
Wherein, metallic catalyst, after decolouring inactivation, the mixed solution drip washing metallic catalyst of the aqueous solution of available organic solvent or pH3-9 or organic solvent and water, removes the pollutant that is attached to metallic catalyst surface. Conventional organic solvent includes but not limited to ethanol, isopropyl alcohol, acetone and the mixture with water.
Wherein, colorful wastewater source includes but not limited to the colorful wastewater of the industries such as pharmacy, papermaking, printing and dyeing, pottery, leather or chemical industry. The pH value scope of application of colorful wastewater is wide, can be from 0-14, and preferably 5-9.
The invention has the beneficial effects as follows:
The invention provides a kind of application of above-mentioned carrier to load metal catalyst. This catalyst has with low cost, and operation controllability is high, and catalytic effect is more efficient, and catalyst stability can keep the features such as recycled for multiple times. This catalyst can be applicable under the effect of reducing agent as effective catalyst but is not limited to the colorful wastewater processing of the industries such as pharmacy, papermaking, printing and dyeing, pottery, leather or chemical industry.
Detailed description of the invention
The preparation process patent applied for of framework material supported catalyst: a kind of preparation method of metal supported catalyst. Preferred embodiment is for filling packed column after clay loaded nano-silver catalyst granulation, add after borane reducing agent sodium hydride and methylene blue mixed solvent, carried out post processing, required bleaching time is 10 seconds-1 hour, use exceedes after 50 times, and percent of decolourization reaches more than 95%. Under the aqueous solution that use contains acetone, carry out drip washing, after drip washing, packed column recovers decoloring ability.
Below by specific embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example. In the situation that not departing from said method thought of the present invention, various replacements or the change made according to ordinary skill knowledge and customary means, all should be within the scope of the present invention. Described method is conventional method if no special instructions. Described material all can obtain from open commercial sources if no special instructions.
Embodiment 1
To after 1g montmorillonite load silver nano-grain catalyst (silver nano-grain that contains 90% imvite, 8% poly-dopamine and 2%) granulation, fill packed column, add after borane reducing agent sodium hydride and methylene blue mixed solution (mass ratio 0.1:1), carried out post processing, required bleaching time is 10 minutes, use exceedes after 50 times, and percent of decolourization reaches more than 95%. The aqueous solution that use contains acetone carries out drip washing, and after drip washing, packed column recovers decoloring ability.
Embodiment 2-6
By 1g talcum powder supported platinum nano beaded catalyst (contain 75% talcum powder, 5% 3,4-dihydroxy benzenes methylamine and 20% Pt nanoparticle) fill packed column after granulation, add after reducing agent hydrazine hydrate or ascorbic acid or polyalcohol or formaldehyde or formic acid and methylene blue mixed solvent (mass ratio 10:1), carried out post processing, required bleaching time is 10 seconds, use exceedes after 50 times, and percent of decolourization reaches more than 95%. Under the aqueous solution that use contains 20% isopropyl alcohol, carry out drip washing, after drip washing, packed column recovers decoloring ability.
Embodiment 7-12
To after 1g montmorillonite load silver nano-grain catalyst (silver nano-grain that contains 90% imvite, 8% poly-dopamine and 2%) granulation, fill packed column, add after borane reducing agent sodium hydride and pharmacy or papermaking or printing and dyeing or pottery or leather or chemical industry mixed solvent colorful wastewater (mass ratio 1:1000), carried out the processing of solid-filling bed, required bleaching time is 1 minute, use exceedes after 100 times, and percent of decolourization reaches more than 95%. The aqueous solution that use contains ethanol carries out drip washing, and after drip washing, packed column recovers decoloring ability.
Embodiment 13-14
To after 1g montmorillonite load gold nano grain catalyst (gold nano grain that contains 90% imvite, 8%DOPA and 2%) granulation, fill packed column, add after borane reducing agent sodium hydride and printing and dyeing colorful wastewaters (mass ratio 1:10000), carried out the processing of solid-filling bed, required bleaching time is 1 minute, use exceedes after 500 times, and percent of decolourization reaches more than 95%. The aqueous solution that use contains 10% ethanol or isopropyl alcohol carries out drip washing, and after drip washing, packed column recovers decoloring ability.
Embodiment 15-21
By the catalyst of 1g polystyrene microsphere supported copper ion (copper ion that contains 90% polysulfones particle, 8%DOPA and 2%) dress packed column, add after borane reducing agent sodium hydride and printing and dyeing colorful wastewaters (mass ratio 1:100), carried out the processing of solid-filling bed, regulation system pH is respectively 0,3,5,9,12,14, required bleaching time all, in 1 minute, uses and exceedes after 100 times, and percent of decolourization reaches more than 95%. The aqueous solution that use contains isopropyl alcohol carries out drip washing, and after drip washing, packed column recovers decoloring ability.
It should be noted last that, above detailed description of the invention is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to example, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. a decoloration treatment method for coloured waste liquid, is characterized in that,
(a) by the metallic catalyst of load and reducing agent for the processing of decolouring fast of coloured waste liquid, required bleaching time is 10 seconds ~ 1 hour, the optimization time is 1 minute ~ 10 minutes;
(b) for the decolouring processing of coloured waste liquid, the metallic catalyst of load and reducing agent (can not limit sequentially) and are distributed in coloured waste liquid the processing of decolouring simultaneously or successively;
(c) for the decolouring processing of coloured waste liquid, the metallic catalyst of load can be dressed up to packed column or be fixed on packed bed, dye solution and reducing agent mixed liquor are flowed through to metallic catalyst simultaneously and decoloured;
(d) for the decolouring processing of coloured waste liquid, dyestuff mass ratio 0.001 ~ 1000 in reducing agent and coloured waste liquid, is preferably 0.01 ~ 100;
(e) for the decolouring processing of coloured waste liquid, the metallic catalyst lasting use capable of circulation of load, once adds; continue to keep active; only need to supplement reducing agent and continue for a long time to process more coloured waste liquid, the decolorizing effect of coloured waste liquid is greater than to 80%, can realize decolorizing effect and be greater than 95%;
(f) for the decolouring processing of coloured waste liquid, the increase metallic catalyst of load and dosage or the consumption of reducing agent, can accelerate decoloring reaction, shortens decolouring required time;
(g) coloured waste liquid can be the aqueous solution, also can be organic solvent, or the mixed solution of organic solvent and water, and selected reducing agent need be dissolved in coloured waste liquid.
2. a kind of decoloration treatment method of coloured waste liquid according to claim 1, it is characterized in that, the metallic catalyst of the load of processing for colorful wastewater decolouring, comprise (a) catalyst backbone carrier material, the polymer coating that (b) catalyst backbone surfaces of carrier materials contains catechol derivatives; (c) play metal or metal oxide or the metal ion of catalytic action, by embedding or boning or be chelated to the polymer coating of catechol derivatives, and then be fixed to catalyst backbone surfaces of carrier materials; Wherein load on the metal of skeleton carrier material surface or metal oxide or metal ion and play catalyst action, for the decolouring processing of coloured waste liquid.
3. according to the decoloration treatment method of a kind of coloured waste liquid described in claim 1 or 2, it is characterized in that, the metallic catalyst of the load of processing for coloured waste liquid decolouring, the quality percentage composition that carrier framework material accounts for described catalyst system is 10-99%, is preferably 75%-95%; The quality percentage composition that metallic catalyst accounts for described catalyst system is 0.1-50.0%, is preferably 1%-20%; The quality percentage composition that described catechol derivative polymer coating accounts for described catalyst system is 0.01-50%, is preferably 0.1-10%.
4. according to the decoloration treatment method of a kind of coloured waste liquid described in claim 2 or 3, it is characterized in that, catalyst backbone carrier material is selected to be had compared with the particle powder of the inorganic material of bigger serface or Inorganic Non-metallic Materials or organic material or sheet material or sheet material, and wherein inorganic material or Inorganic Non-metallic Materials include but not limited to the (imvite of clay class, tired de-soil, diatomite, bentonite, attapulgite, kaolin, atlapulgite, zeolite, illite, galapectite, vermiculite, serpentine etc.), sandstone class (river sand, extra large sand, metal sand, the sand after natural sandstone efflorescence etc.), stone flour class (medical stone powder, dicalcium powder, talcum powder, dolomite dust, powder of lacquer putty for use on etc.), flyash, flue dust, metal and oxide thereof or hydroxide (aluminium salt, molysite, magnesium salts, silicon salt, titanium salt and complex salt etc. thereof, conventional have alum, aluminium polychloride, PAFC, poly-ferric chloride, polymer phosphate aluminium, polymer aluminium silicate, polymeric aluminium ferrum silicate, calcium aluminate, manganese oxide, iron oxide, aluminium oxide, zirconia, antimony oxide, calcium carbonate, zinc oxide, magnesium hydroxide) etc. one or more, wherein organic material includes but not limited to starch and starch Deformation Products, active carbon, Graphene and Graphene derivative, CNT and derivative thereof, polymer microsphere and powder or diaphragm are (as polyethylene, polypropylene, polysulfones, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylamide, polyaniline, polystyrene, cellulose and derivative thereof).
5. the decoloration treatment method of a kind of coloured waste liquid according to claim 2, is characterized in that, described catechol analog derivative is a kind of organic molecule that contains dihydroxy benzenes base section and derivative thereof, and its general molecular formula is:
Include but not limited to following molecular formula:
Wherein R1, R2, R3, R4, R5 is identical or different, be selected from independently of one another hydrogen, saturated and undersaturated, straight chain and side chain, replacement and unsubstituted C1-10 alkyl, and contain amino, carboxyl, sulfydryl, one or more substituents in halogen, oh group, low-grade alkyl group, lower alkoxy groups, monocyclic aryl, lower acyl group and their combination; Including, but not limited to DOPA (DOPA), dopamine and salt, 3 thereof, 4-dihydroxy benzenes methylamine, 3,4-4-dihydroxy benzaldehyde, 3,4-dihydroxy benzenes acetaldehyde, PCA or DOPAC.
6. according to the decoloration treatment method of a kind of coloured waste liquid described in claim 2 or 3, it is characterized in that, described metal or metal oxide or metal ion include but not limited to copper, silver, titanium, platinum, gold etc.
7. the decoloration treatment method of a kind of coloured waste liquid according to claim 1, is characterized in that, described reducing agent includes but not limited to sodium borohydride, hydrazine hydrate, ascorbic acid, polyalcohol, formaldehyde and formic acid etc.
8. the decoloration treatment method of a kind of coloured waste liquid according to claim 1, is characterized in that, the metallic catalyst of described load can fill packed column or be fixed to packed bed for colorful wastewater decolouring processing after granulation.
9. the decoloration treatment method of a kind of coloured waste liquid according to claim 1, it is characterized in that, the metallic catalyst of described load, after decolouring inactivation, the mixed solution drip washing metallic catalyst of the aqueous solution of available organic solvent or pH3-9 or organic solvent and water, the pollutant on the metallic catalyst surface of load is adhered in removal, and conventional organic solvent includes but not limited to ethanol, isopropyl alcohol, acetone and the mixture with water.
10. a kind of decoloration treatment method of coloured waste liquid according to claim 1, it is characterized in that, described coloured waste liquid source includes but not limited to coloured waste liquid of the industries such as pharmacy, papermaking, printing and dyeing, pottery, leather or chemical industry, and the pH value scope of application of coloured waste liquid is wide, can be from 0-14.
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| CN106540691A (en) * | 2016-09-30 | 2017-03-29 | 天津宝兴威科技有限公司 | A kind of preparation method of nano-silver catalyst |
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| CN107282082A (en) * | 2017-06-15 | 2017-10-24 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr（Ⅵ）Application in liquid phase catalytic reduction |
| CN108176356A (en) * | 2017-12-31 | 2018-06-19 | 安徽万方织染有限公司 | A kind of preparation process of environmentally protective high adsorption activity dyeing waste water adsorbent |
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| CN106540691A (en) * | 2016-09-30 | 2017-03-29 | 天津宝兴威科技有限公司 | A kind of preparation method of nano-silver catalyst |
| CN106830163A (en) * | 2017-02-13 | 2017-06-13 | 安徽其霖环境工程技术有限公司 | A kind of Industrial Waste Water Treatments adsorbent |
| CN107282082B (en) * | 2017-06-15 | 2020-04-28 | 南京大学 | Supported noble metal catalyst with coating structure, preparation method thereof and application thereof in Cr (VI) liquid phase catalytic reduction |
| CN107282082A (en) * | 2017-06-15 | 2017-10-24 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and in Cr（Ⅵ）Application in liquid phase catalytic reduction |
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