CN1962470A - Inner electrolytic material for treating waste water difficult for biological degradation and its preparation method - Google Patents
Inner electrolytic material for treating waste water difficult for biological degradation and its preparation method Download PDFInfo
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- CN1962470A CN1962470A CNA2006101298776A CN200610129877A CN1962470A CN 1962470 A CN1962470 A CN 1962470A CN A2006101298776 A CNA2006101298776 A CN A2006101298776A CN 200610129877 A CN200610129877 A CN 200610129877A CN 1962470 A CN1962470 A CN 1962470A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses an inner electrolytic material and preparing method of biological difficult-degradation waste water, which comprises the following parts: 50-85% iron filling, 5-50% macromolecular resin (polyethylene resin, polypropylene resin and polyurethane) and 0.2-30% macromolecular resin monomer (epoxide resin and acrylate), wherein the inner electrolytic material can prevent iron filling from rusting into block, which makes iron filling suspend in the water. The invention maintains excellent mass transfer condition and electrochemical property on the iron filling surface, which reduces fluidization energy consumption.
Description
Technical field
The present invention relates to the environmental protection water technology, particularly a kind of inner electrolytic material and preparation method who is used to handle waste water difficult for biological degradation.
Background technology
For containing high density and being difficult to the organic waste water of biological degradation; the general materilization freatment methods such as oxidation (as photochemical catalytic oxidation, chemical oxidation---Feton method, ozone method, radiation oxidation, supercritical oxidation etc.), electrolysis and membrane technique that adopt; the processing cost height of common these methods; facility investment is big; especially processing (as waste water such as printing and dyeing, the chemical industry) processing cost for big flow waste water is higher more outstanding, and the processing cost height has become the bottleneck of environment protection cause.
Biochemical process is the method for common most economical and effective wastewater treatment of generally acknowledging at present.But many high-enriched organics trade effluents (as printing and dyeing, dyestuff and pharmacy etc.) that contain are difficult to biological degradation, also are difficult to handle with the general physical chemical process.In recent years, because of electrolytic electrochemical process for treating cost in the waste iron filing is lower, effect is better, and experimental study is very active.
Electrolytic processing method can reduce COD (COD clearance 25～80%) to printing and dyeing, azo dyes, reactive dyestuffs, DYE PRODUCTION comprehensive wastewater in the waste iron filing, and is very outstanding to the high concentration waste water in dye production decoloration performance, percent of decolourization height (50～99%); To electroplating wastewater (as chromic reduction), it is good that the pollutent of many Toxics such as alcohol waste water, dinitrochlorobenzene, two chlorophenol waste water, hydrochloric ether, difficult for biological degradation has a treatment effect, the advantage that cost is low.
(the application test research of iron filings in waste water in dye production is handled such as Tong Ling; " renewable resource research " 1 phase in 2005); (the zeroth order iron processes is handled reactive brilliant orange X-GN waste water from dyestuff Tsing-Hua University's journal " natural science edition " 2005 to Yang Ying etc.; 45 (3): 359～362; 366) and the disclosed electrochemical process for treating of Yu Feng etc. [H acid comprehensive wastewater administers process test research and engineering is used " environmental protection science " 1999 26 (4)] mainly be to use iron filings; carbon granules; coke and flyash are as inner electrolytic material (or filler), with the form operation of stationary bed (trickle bed) or filter bed.
Prior art subject matter is: the surface passivation of iron filings after operation for some time (or the high iron ball of carbon content, concave-convex shaped iron material etc.) filler, must acid activation, but iron filings become rusty into entity, the low activation difficulty of voidage.Its key issue is the carrying out with little original battery electrochemistry reaction, the oxide compound of sedimentary carbon of iron surface (can not remove with acid) and iron is more and more, the electropotential of the negative electrode of galvanic cell (polarization) raises, waste water mass transfer situation degenerates, thereby its processing efficiency obviously reduces, and the iron filler become rusty into bulk sometimes in addition with equipment rust together.Therefore, many enterprises (as Ningbo of Zhejiang dye chemical industry factory, Anhui Fengyang Dyestuff Chemical Co., Ltd.) treatment effect that brings into operation is better, and processing efficiency obviously reduces gradually, does not almost have treatment effect afterwards so that at last that it is out of service.
In addition, (non-ferrous metal 17 2 phases of volume of March calendar year 2001) such as disclosed iron filings fluidized-bed such as Xie Juan pre-treatment-catalyzed oxidation-coagulating sedimentation combination process processing organic silicon wastewater (chemical industry environmental protection 26 1 phases of volume of February in 2006) and Zhan Chaohui disclose the art treatment that rotates the electrolysis process dye wastewater treatment using that declines, main drawback wherein be because of iron filings than great, fluidisation energy consumption height; When the iron filings fluidisation or rotate, big to equipment attrition.
Summary of the invention
The purpose of this invention is to provide a kind of inner electrolytic material and preparation method who is used to handle waste water difficult for biological degradation, can overcome the shortcoming of prior art.Electrolytic electrochemical process for treating can prevent that the iron filings filler from becoming rusty into bulk in the waste iron filing of the present invention, even with equipment rust problem together, make the iron filings filler can be suspended in the water, the oxide compound that helps sedimentary carbon of iron surface (can not remove with acid) and iron is in time removed down with good mass transfer conditions and the chemical property in maintenance iron filings surface flowing of water, and reduces the fluidisation energy consumption.
The inner electrolytic material that the present invention is used to handle waste water difficult for biological degradation comprises that iron filings, macromolecule resin and macromolecule resin monomer are that mixed raw material forms fully, and their weight percent is formed and is:
Macromolecule resin 5～50%
Macromolecule resin monomer 0.2～30%.
Said macromolecule resin monomer is Resins, epoxy and acrylate, weight percent: 35-50%: 50-65%.Said acrylate is methacrylic acid divinyl ester or methyl methacrylate etc.
Said macromolecule resin is to choose any one kind of them at least in polyvinyl resin, polystyrene resin, acrylic resin and the urethane or two kinds.The weight percent composition is in the said macromolecule resin:
Polyvinyl resin 0.3～50%
Polystyrene resin 1～95%
Urethane 3.5～95%
Acrylic resin 0.2～30%
The selectable macromolecule resin prescription of the present invention:
Said macromolecule resin is urethane, acrylic resin and polyvinyl resin.
Said macromolecule resin is polyvinyl resin and acrylic resin.
Said macromolecule resin is urethane and polyvinyl resin.
Said iron filings are grey cast iron or spheroidal graphite cast iron.
The preparation method of the said inner electrolytic material of the present invention is through following step: under 5～50 ℃ of temperature, macromolecule resin and macromolecule resin monomer etc. is added reactor successively, mix, 0～45 ℃ was reacted 2～60 minutes, add iron filings, the reaction 4～30 hours down of 0～50 ℃, 0.1～0.3Mpa.
Inner electrolytic material of the present invention can be suspended in the water or with the very low water pump of lift (as the 1.5m water column) can make its suspension, helps that iron surface is sedimental in time to be removed, and prevents from that iron filings from getting rusty to form hard bulk; The present invention can be suspended in the water, and proportion is little, the energy consumption when therefore greatly reducing fluidisation.Specifically, because known technology is that iron filings or iron filings, carbon granules, coke and flyash are as inner electrolytic material (filler), as form operation with stationary bed (trickle bed) or filter bed, the surface passivation of iron filings after operation for some time (or the high iron ball of carbon content, concave-convex shaped iron material etc.) filler, easily become rusty into entity, the low activation difficulty of voidage, and even lose activity with the equipment rust together.As the form operation with fluidized-bed, energy consumption is big, and is big to equipment attrition; Iron filings and carbon granules, coke and flyash proportion differ greatly (about 5～8 times) in addition, fluidization conditions is difficult to determine, carbon granules, coke and flyash critical fluidization velocity are far smaller than the critical fluidization velocity of iron filings, and fluidisation causes the segregation section of carbon granules, coke and flyash and iron filings; When fluidisation degree hour, iron filings are concentrated and the formation bulk of getting rusty.Inner electrolytic material of the present invention (iron filings filler) proportion is little, can be suspended in the water or and can make its suspension with the very low water pump of lift (as the 1.5m water column), both helped that iron surface is sedimental in time to be removed, prevented get rusty energy consumption when forming hard bulk and can reduce fluidisation greatly again of iron filings.
Only with regard to China's textile printing and dyeing industry, many organism are arranged in the dyeing waste water, biodegradability is poor.After many scale wastewater treatment colourity, COD still difficulty reach enterprise, national specified discharge standard.According to incompletely statistics, the annual waste discharge amount of textile printing and dyeing industry reaches more than 900,000,000 ton, and wherein to account for 80% of textile waste quantity discharged be that annual waste discharge amount reaches more than 7.2 hundred million ton to the dyeing waste water quantity discharged, occupies the 6th of China's discharged volume of industrial waste water.Complicated more, the biodegradability difference of pollutent and be difficult to handle in the industry production waste water such as dyestuff, pharmacy and chemical industry.If utilize the iron filings inner electrolytic material that suspends of the present invention, can make the interior electrolysis treatment method for waste water through engineering approaches that processing cost is low, processing efficiency is high.If dyeing waste water this method of 20%, just can handle more than 1.4 hundred million ton of waste water every year, and this only is a dyeing waste water, does not also consider the waste water of other industry.Therefore, the present invention has significant effect and economic and social benefit.
Description of drawings
Fig. 1 is a dye processing plant comprehensive wastewater treatment effect.
Embodiment
The urethane (polymkeric substance of toluene diisocyanate or poly methylene poly phenyl poly isocyanate and propylene glycol) that the present invention uses, molecular weight 2000～5000; Polystyrene resin molecular weight: 45000～63000; The polyvinyl resin molecular weight: 200～5,000,000, molecular weight of epoxy resin: 400～700, acrylic resin molecular weight: 20～400,000; Acrylate is: methacrylic acid divinyl ester, methyl methacrylate etc.
Iron filings pre-treatment:, remove its surface and oil contaminant with 1～4%NaOH aqueous solution soaking iron filings.Water or 1～2%HCl aqueous solution wash to neutrality or slightly acidic (pH=5～7) again.
Example 1: at 5 ℃ with polyvinyl resin (molecular weight 25000) 10g, urethane 15g (dimethylene phenylbenzene tetraisocyanate and glycol polymers, molecular weight 5000), add successively and mix in the reactor, 15 ℃ of reactions are 2 minutes with Resins, epoxy 2g, methyl methacrylate 2g etc.Add grey cast iron iron filings 55g, reaction is 10 hours under 50 ℃, 0.15Mpa.
Example 2: at 10 ℃ with urethane 10g (tolylene diisocyanate and glycol polymers molecular weight 4500), acrylic resin 5g (molecular weight 30000), polyvinyl resin 10g (molecular weight 5000) (molecular weight 5000), Resins, epoxy 2g, methacrylic acid divinyl ester 5g etc. adds successively and mixes in the reactor, 25 ℃ were reacted 2 minutes, add spheroidal graphite cast iron iron filings 60g, reaction is 8 hours under 40 ℃, 0.2Mpa.
Example 3: 8 urethane 13g (dimethylene phenylbenzene tetraisocyanate and glycol polymers molecular weight 5000), polyvinyl resin 2g (molecular weight 20000), Resins, epoxy 3g, methyl methacrylate 5g etc. are added successively and to mix in the reactor, 5 ℃ were reacted 8 minutes, add iron filings 50g, reaction is 4 hours under 10 ℃, 0.3Mpa.
Example 4: at 5 ℃ with polystyrene resin 10g (molecular weight 50000); Urethane 12g (dimethylene diphenyl diisocyanate molecular weight 5000); , add successively and mix in the reactor with Resins, epoxy 2g, methyl methacrylate 2g etc., 15 ℃ of reactions 2 minutes.Add grey cast iron iron filings 55g, reaction is 10 hours under 50 ℃, 0.15Mpa.
Example 5: 5 ℃ with polyvinyl resin 5g (molecular weight 50000), urethane 15g (dimethylene diphenyl diisocyanate and glycol polymers molecular weight 4500), add successively and mix in the reactor with Resins, epoxy 2g, methyl methacrylate 2g etc., 15 ℃ of reactions 2 minutes.Add grey cast iron iron filings 60g, reaction is 20 hours under 30 ℃, 0.12Mpa.
Use sample of the present invention (example 1) to see Fig. 1 for dye processing plant, Tianjin (producing dyestuffs such as activity, acidity, slightly acidic, metal complex) comprehensive wastewater decolouring treatment effect.The decolouring treatment effect is weighed with chromaticity index.Colourity is measured with extension rate method (the mensuration GB 11903-89 of water quality colourity).Instrument: 50mL colorimetric cylinder etc.Chroma removal rate is calculated as:
Chroma removal rate %=(former colority of water/doubly-colourity after handling/doubly) the former colority of water of ÷/doubly * 100.
The suspension characteristic of sample of the present invention is with proportion and its suspension situation check in water.
Specific weight determine instrument: balance, volumetric flask, transfer pipet.Volumetric flask is filled to scale (constant volume), after sample of the present invention (be weighed as W gram) put into volumetric flask, liquid level rises, and with transfer pipet the water of volumetric flask scale with top is gone in the dried beaker (weighing), and weighing and calculate this portion water with method of addition is W
0Gram.Being calculated as of sample proportion of the present invention: proportion=W/W
0
The suspension characteristic of sample of the present invention illustrates in the stationary water neutralization reactor respectively.
Sample of the present invention (100g) is placed in the beaker of 1000mL (having added 600mL water), the suspension situation of observation sample sees Table 1.
Table 1 sample physical property of the present invention table
| The sample sequence number | Proportion | Suspension situation in the stationary water | The sample sequence number | Proportion | Suspension situation in the stationary water |
| 1 (example 1) | 0.98 | Suspend | 4 (examples 4) | 0.99 | Suspend |
| 2 (examples 4) | 0.99 | Suspend | 5 (examples 5) | 1.10 | Do not suspend |
| 3 (examples 2) | 1.01 | Do not suspend | 6 (examples 3) | 1.05 | Do not suspend |
The suspension characteristic of sample in flowing water: it is that 100mm is high in the reactor of 300mm that sample of the present invention No. 3 (200g) is placed on diameter, with (2.7 meters of lifts, 8 liters/minute of flows) water pump makes water pass through reactor (seeing synoptic diagram 2), and the suspension situation of observation sample sees Table 2.
Get former iron filings (without the technology of the present invention processing) 200g to be placed on diameter be that 100mm is high and make water pass through reactor in the reactor of 300mm with (2.7 meters of lifts, 8 liters/minute of flows) water pump, iron filings can not suspend.
Table 2 sample of the present invention is in mobile water performance
| The sample sequence number | Proportion | The suspension situation | The sample sequence number | Proportion | The suspension situation |
| 1 (example 1) | 0.98 | Suspend | 4 (examples 4) | 0.99 | Suspend |
| 2 (examples 4) | 0.99 | Suspend | 5 (examples 5) | 1.10 | Suspend |
| 3 (examples 2) | 1.01 | Suspend | 6 (examples 3) | 1.05 | Suspend |
Claims (10)
1, a kind of inner electrolytic material that is used to handle waste water difficult for biological degradation is characterized in that it comprises that iron filings, macromolecule resin and macromolecule resin monomer are that mixed raw material forms fully, and the weight percent composition is:
Iron filings 50～85%
Macromolecule resin 5～50%
Macromolecule resin monomer 0.2～30%.
2,, it is characterized in that said macromolecule resin monomer is Resins, epoxy and acrylate according to the said inner electrolytic material of claim 1.
3,, it is characterized in that the weight percent of said Resins, epoxy and acrylate: 35-50%: 50-65% according to the said inner electrolytic material of claim 2.
4,, it is characterized in that said acrylate is methacrylic acid divinyl ester or methyl methacrylate according to the said inner electrolytic material of claim 2.
5,, it is characterized in that said macromolecule resin is to choose any one kind of them at least in polyvinyl resin, polystyrene resin, acrylic resin and the urethane or two kinds according to the said inner electrolytic material of claim 1;
The weight percent composition is in the said macromolecule resin:
Polyvinyl resin 0.3～50%
Polystyrene resin 1～95%
Urethane 3.5～95%
Acrylic resin 0.2～30%
6,, it is characterized in that said macromolecule resin is urethane, acrylic resin and polyvinyl resin according to the said inner electrolytic material of claim 5.
7,, it is characterized in that said macromolecule resin is polyvinyl resin and acrylic resin according to the said inner electrolytic material of claim 5.
8,, it is characterized in that said macromolecule resin is urethane and polyvinyl resin according to the said inner electrolytic material of claim 5.
9,, it is characterized in that said iron filings are grey cast iron or spheroidal graphite cast iron according to the said inner electrolytic material of claim 1.
10, the preparation method of the said inner electrolytic material of claim 1, it is characterized in that it is through following step: under 5～50 ℃ of temperature, macromolecule resin and macromolecule resin monomer etc. is added reactor successively, mix, 0～45 ℃ was reacted 2～60 minutes, add iron filings, the reaction 4～30 hours down of 0～50 ℃, 0.1～0.3Mpa.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101298776A CN100469706C (en) | 2006-12-05 | 2006-12-05 | Inner electrolytic material for treating waste water difficult for biological degradation and its preparation method |
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| CNB2006101298776A CN100469706C (en) | 2006-12-05 | 2006-12-05 | Inner electrolytic material for treating waste water difficult for biological degradation and its preparation method |
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| CN1962470A true CN1962470A (en) | 2007-05-16 |
| CN100469706C CN100469706C (en) | 2009-03-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955279A (en) * | 2010-07-13 | 2011-01-26 | 同济大学 | Advanced treatment method of industrial waste water by combining catalysis internal electrolysis, coupling, oxidization and flocculation |
| CN102174253A (en) * | 2011-01-29 | 2011-09-07 | 浙江省环境保护科学设计研究院 | Preparation method and application of porous hydrophilic denitrification biological carrier |
| CN101759329B (en) * | 2010-01-08 | 2012-04-25 | 蓝星环境工程有限公司 | Method for processing organosilicon waste water |
| CN103936225A (en) * | 2014-03-24 | 2014-07-23 | 同济大学 | Coke wastewater advanced treatment method utilizing catalytic internal electrolysis technology and coupled two-stage bio-filter |
-
2006
- 2006-12-05 CN CNB2006101298776A patent/CN100469706C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759329B (en) * | 2010-01-08 | 2012-04-25 | 蓝星环境工程有限公司 | Method for processing organosilicon waste water |
| CN101955279A (en) * | 2010-07-13 | 2011-01-26 | 同济大学 | Advanced treatment method of industrial waste water by combining catalysis internal electrolysis, coupling, oxidization and flocculation |
| CN102174253A (en) * | 2011-01-29 | 2011-09-07 | 浙江省环境保护科学设计研究院 | Preparation method and application of porous hydrophilic denitrification biological carrier |
| CN103936225A (en) * | 2014-03-24 | 2014-07-23 | 同济大学 | Coke wastewater advanced treatment method utilizing catalytic internal electrolysis technology and coupled two-stage bio-filter |
| CN103936225B (en) * | 2014-03-24 | 2016-02-17 | 同济大学 | The method of catalyzed internal electrocatalysis coupling two-stage biofilter advanced treatment on coking wastewater |
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| Publication number | Publication date |
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| CN100469706C (en) | 2009-03-18 |
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Granted publication date: 20090318 Termination date: 20100105 |