CN101456644A - Method for processing organic industrial effluent by catalytic reduction bio-ferric technique - Google Patents
Method for processing organic industrial effluent by catalytic reduction bio-ferric technique Download PDFInfo
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- CN101456644A CN101456644A CNA2007101986272A CN200710198627A CN101456644A CN 101456644 A CN101456644 A CN 101456644A CN A2007101986272 A CNA2007101986272 A CN A2007101986272A CN 200710198627 A CN200710198627 A CN 200710198627A CN 101456644 A CN101456644 A CN 101456644A
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Abstract
The invention relates to a method for treating organic industrial wastewater by catalytic reduction biological iron technology. The method comprises: wastewater is subjected to steps of anaerobic treatment, aerobic treatment and sedimentation treatment. The method is characterized in that the step of anaerobic treatment comprises: a reactor filled with a filler is arranged in a pipeline of treated wastewater or is positioned in an anaerobic tank of the treated wastewater so that the treated wastewater has redox reaction in the process of filling in reaction; zero valent iron is continuously oxidized and dissolved out; ferric ions are continuously released in the wastewater of a biochemical pool to form biological ferric sludge, thereby achieving the biochemical treatment effect of strengthening wastewater; and the filler is iron, iron and copper or iron, copper and an active carbon catalyst. The method can improve the prior biochemical treatment technology and reach the aim of treating nondegradable organic industrial wastewater through a biochemical iron strengthening method; and compared with the prior biochemical treatment technology, the removing rate of organic pollutants and chroma in the wastewater can be improved by 10 to 40 percent.
Description
Technical field
The present invention relates to method of wastewater treatment, particularly relate to a kind of method of catalytic reduction enhanced biological iron technical finesse refractory organic industrial sewage.
Background technology
Many industrial enterprises as industries such as refining of petroleum, coking, chemical fibre, dyestuff, chemical fertilizer, papermaking, pharmacy, food, give off the waste water that contains organic pollutant in a large number in process of production, and wherein a lot of pollutents are hardly degraded organic substance.These materials have toxicity mostly and are difficult to effectively to be removed by traditional biology and physical chemistry method, in case after entering water body, will be to Human's production, life and the serious harm of healthy generation.
At present, the method that the processing refractory organic industrial sewage the most generally adopts is a biochemical process, especially anaerobism (anoxic)-aerobic process (A-0 method or A-A-0 method).Because some organism is difficult to by the increasingly stringent of biological degradation and pollutant emission standard, the traditional biochemical processing of single employing can not satisfy the requirement to environmental quality fully.
Summary of the invention
The method that the purpose of this invention is to provide a kind of processing organic industrial effluent by catalytic reduction bio-ferric technique.The inventive method is a kind of a kind of novel method of handling the organic industrial sewage of difficult degradation with catalytic reduction enhanced biological iron technology, be used to improve traditional biochemical processing, reach the purpose of handling the organic industrial sewage of difficult degradation with the enhanced biological iron processes, the removal efficient of organic pollutant in the waste water and colourity can significantly improve.
The objective of the invention is to realize by following technical scheme.The inventive method comprises waste water through anaerobic treatment, aerobic treatment and precipitation process step, it is characterized in that described anaerobic treatment step is: the reduction reactor that filler will be housed is installed in the pipeline of processed waste water, or place in the anaerobic pond of processed waste water, make processed waste water in the process process of these fillers, redox reaction takes place, Zero-valent Iron constantly is oxidized to ferrous ion and stripping from reactor, some organism in the waste water is reduced simultaneously, discharge iron ion in the waste water of reactor in the anaerobic pond biochemistry pool continuously, form biological iron mud, reach the biochemical treatment effect of strengthening waste water; Described filler is an iron; Or the mixture of iron and copper; Or the mixture of iron, copper and activated carbon catalyst.
Between described aerobic treatment step and precipitation process step, has reflow step; And/or between described anaerobic treatment step and aerobic treatment step, has reflow step when waste water need be removed ammonia nitrogen (if, between anaerobic treatment step and aerobic treatment step, adopt reflow step).
In described reflow step, processed waste water is 100-400% from the aerobic treatment pond to the reflux ratio in anaerobic treatment pond; Mud is 50-200% from the precipitation process pond to the reflux ratio that aerobic treating pond refluxes.In described redox reaction, the iron concentration in the waste water in the described anaerobic biological pond remains on 5-50mg/L.
The making method of described activated carbon catalyst may further comprise the steps:
1) with activated carbon 10%NaOH solution soaking, filtration, is washed till neutrality with deionized water;
2) soak, filter with the HCl dissolving of 1:1 again, be washed till neutrality with deionized water, dry in baking oven;
3) with above-mentioned substance at the Cu of 0.2～0.4mol/L (NO
3)
2Stir in the solution, drip 20% NaHCO
3Precipitation agent gets copper-containing substance; Or above-mentioned substance is placed the FeCl of 0.05～2.5mol/L
3Stir in the solution, get iron compound;
4) with described copper-containing substance or iron compound respectively through slaking, filtration, separate out with deionized water rinsing to non-metallic ion, be put in the baking oven dry; Obtain the copper-loaded solid of activated carbon of modification or the activated carbon of modification and carry the iron solid;
5) activated carbon of copper-loaded solid of the activated carbon of described modification or modification is carried the iron solid and activate respectively, make described activated carbon catalyst, i.e. the activated carbon of copper-loaded catalyzer of the activated carbon of modification or modification carries iron catalyst.
The filling mass ratio of the filler in the described reduction reactor is: iron: copper: activated carbon catalyst=100%:0%～50%:0%～15%.
The porosity of described reaction filler is 30%～70%.
The present invention mainly comprises the technology of preparing of catalytic reduction technology and biological iron technology and activated carbon catalyst.
The catalytic reduction technology mainly is to utilize the redoxomorphism of iron.Zero-valent Iron is good reductive agent to some organism, Zero-valent Iron generation oxidizing reaction in the reactor generates ferrous iron, with speed per hour advance some organism in the waste water be reduced into easy degraded than small-molecule substance, thereby improved the biodegradability of waste water and reduced colourity, alleviated the load of subsequent biological treatment.
Biological iron technology mainly is the iron ion that utilizes reduction reactor to produce, and improves the efficient of biological treatment.In anaerobism (anoxic) pond, iron mainly is that the form with FeS exists, and FeS is the important component of a lot of anaerobic reaction enzymes of catalysis.Having of small amounts of iron helps stable particle mud structure, makes that the superiority of methanobacteria changes in the pond, improved the speed of utilizing of acetate.In Aerobic Pond, iron is oxidized to ferric iron.Iron is the important component part of cytopigment in the bio-oxidation enzyme system, and dehydrogenase activity is had promoter action.Ferric iron is good flocculation agent simultaneously, has improved the bio-oxidation and the biological flocculation of active sludge greatly.
The present invention adopts and is mixed into the reaction filler with the copper-loaded iron catalyst of the activated carbon of iron, copper and modification, waste water is flowed through react filler generation redox reaction, reaches the effect of enhanced biological iron technical finesse waste water.Because iron is by fe, Fe
3C and some impurity are formed, and when it was in the electrolyte solution, itself can form numerous microcosmic corrosion cell, and redox reaction takes place.And the copper of iron and adding has constituted a series of galvanic cell reaction system, and wherein iron is anode, is the negative electrode of galvanic cell for the system reaction provides electronics, copper.The gac of modification can constitute macroscopical electrode with iron, and the mass transfer process of these pollutents to electrode surface quickened in the adsorption and enrichment effect of organic pollutant and heavy metal, has further improved treatment effect.Metallic iron and copper packing as the reaction filler can be arbitrary shape or some leftover bits such as sheet, wood shavings, chip, in the different shape reactor made from metallic copper of also activated carbon catalyst of iron and modification directly can being packed into.During use, generally be when being used for the stronger waste water of corrodibility and oxidisability, only to load fe in the reduction reactor; Be used for other class refractory organic industrial sewage, load iron and copper in the reduction reactor, or load the activated carbon catalyst of iron, copper and modification.The reduction reactor that filling is good directly is installed in the waste pipe and/or places in anaerobism (anoxic) biochemistry pool.
The adding of activated carbon catalyst has improved processing efficiency.
The technical process of present method as shown in Figure 1.
Advantage of the present invention is as follows:
The present invention utilizes the reaction filler in the reactor to handle a kind of effective novel process of organic industrial sewage with enhanced biological iron technology, and its mechanism is reaction filler, microorganism and the coefficient result of waste water.
1, the present invention has fully utilized redox and biological iron technology, has strengthened the ability of the degradable organic pollutant of biochemical treatment system greatly, and decolorizing effect is obvious.
2, reduction reactor is installed in Waste Water Treatment, can make the continuous stripping of iron ion and in biochemistry pool, keep certain concentration, promote the anaerobic and aerobic microorganisms to the decomposition of organic pollutant and improved the sedimentation function of mud, increased substantially the processing efficiency of refractory organic industrial sewage.
3, the use of activated carbon catalyst has improved the specific surface area and the catalytic effect of reaction medium; the mass transfer process of pollutent to electrode surface quickened in the adsorption and enrichment effect of pollutent; can directly remove the part pollutent in the waste water, and play the effect of guard electrode material.
4, reactor can be square or right cylinder, and material can be used stainless steel, carbon steel or plastics, makes simply, is easy to install, and is easy and simple to handle.The preparation of activated carbon catalyst is simple and easy to do, and recyclable; Iron is cheap, can adopt the waste material of metal works processing; Copper belongs to one-time investment as the basic no consumption of negative electrode of reaction.But the reduction reactor long-time running does not produce the problem that filler lumps substantially.
5, the technology of the present invention does not all have particular requirement to operational conditionss such as the pH value of waste water, temperature, dissolved oxygen contents, and the scope of application is big, does not increase power consumption.Be not only applicable to newly-built waste water processing station, more be specially adapted to the transformation of existing Waste Water Treatment.
6, the present invention is applied widely, adopts different reduction reactors according to different wastewater properties, reaches the purpose of handling refractory organic industrial sewage with the enhanced biological iron processes.
Evidence is compared with conventional biological treatment, adopts the inventive method and existing method relatively, and the removal efficient of organic pollutant and colourity can improve 10-40% in the waste water.
In sum, present method can be improved traditional biochemical processing, reaches the purpose of handling refractory organic industrial sewage with the enhanced biological iron processes, and the removal efficient of organic pollutant and colourity can significantly improve in the waste water.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
Embodiment 1: the processing of the wastewater from chemical industry of oxygenant is contained in the somewhere
At first waste water is pumped into equalizing tank, enter anaerobic fixed film reactor, aerobic aeration pond and settling tank more successively.The reduction reactor that the iron plane flower is housed is installed in the hydrolytic tank, and the porosity of filler is 30%, and iron concentration is controlled at 10mg/L in the pond.The mud of settling tank is back to the aeration tank, and reflux ratio is 80%.
Result is listed in table 1 (mean value).
| Analysis project | Water inlet | Water outlet | Clearance |
| COD cr(mg/L) | 1016.4 | 152.7 | 85.0％ |
| BOD 5(mg/L) | 471.5 | 10.8 | 97.7％ |
Embodiment 2: the processing of somewhere coking chemical waste water
Biological treatment system adopts A-O
2Technology, i.e. one section anaerobic treatment and two sections aerobic treatment.Iron and copper that mass ratio is 100%:30% are housed in the reduction reactor, and the porosity of filler is 50%, and iron concentration is controlled at below the 20mg/L in the pond.Reduction reactor is installed in the anaerobic pond; The mixed-liquor return of aeration tank is to anaerobic pond, and reflux ratio is 300%; The mud of settling tank is back to the aeration tank, and reflux ratio is 100%.Wastewater treatment the results are shown in Table 2:
| BOD 2(mg/L) | COD (mg/L) | NH 3-N (mg/L) | Colourity (NTU) | pH | |
| Water inlet | 1051 | 3094 | 266 | 730 | 7.5 |
| Water outlet | 21 | 148 | 13 | 56 | 6.8 |
| Clearance | 98.0％ | 95.2％ | 95.1％ | 92.3％ |
Embodiment 3: the processing of somewhere food waste liquid
Treatment scheme is: water collecting basin-anaerobic reactor-aeration tank (aerobic)-settling tank-water outlet.
Anaerobic reactor is upflow anaerobic sludge blanket reactor (UASB), and the ring-like filler of plastics is housed in the aeration tank.Copper-loaded or iron catalyst is that 100%:15%:5% mixes by mass ratio with iron, copper and activated carbon, places reduction reactor, and the porosity of filler is 60%, and iron concentration is controlled at below the 20mg/L in the pond.Reduction reactor is installed in the water inlet pipe of anaerobic reactor.Influent waste water COD
CrBe 5500mg/L, BOD
5Be 1780mg/L.Handle the COD in the draining of back
CrBe 327mg/L, clearance is 94%.
Embodiment 4 preparation activated carbon catalysts, according to the following steps:
1) activated carbon is used 10%NaOH solution soaking 24h after-filtration, be washed till neutrality with deionized water;
2) soak the 24h after-filtration with 1:1 HCl dissolving again, be washed till neutrality with deionized water, 105～120 ℃ of dryings in baking oven;
3) with above-mentioned substance at the Cu of 0.2～0.4mol/L (NO
3)
2Fully stir the NaHCO of back dropping 20% in the solution
3Precipitation agent gets copper-containing substance; Perhaps above-mentioned substance is placed the FeCl of 0.05～2.5mol/L
3Fully stir 1h in the solution, get iron compound;
4) with above-mentioned copper-containing substance or iron compound respectively through 24h slaking after-filtration, separate out with deionized water rinsing to non-metallic ion, be put in 105～120 ℃ of dry 6h in the baking oven, obtain the copper-loaded solid of activated carbon of modification or the activated carbon of modification and carry the iron solid.
5) under 260～280 ℃:, make the copper-loaded catalyzer of activated carbon of modification with the copper-loaded solid activation of the activated carbon of modification 2.5h; Or the activated carbon of modification carried iron solid activation 12h, the activated carbon that makes modification carries iron catalyst.
Claims (7)
1, a kind of method of processing organic industrial effluent by catalytic reduction bio-ferric technique, comprise waste water through anaerobic treatment, aerobic treatment and precipitation process step, it is characterized in that described anaerobic treatment step is: the reactor that filler will be housed is installed in the pipeline of processed waste water, or place in the anaerobic pond of processed waste water, make processed waste water in the process process of described filler, redox reaction takes place, and reaches the biochemical treatment effect of strengthening waste water; Described filler is an iron; Or the mixture of iron and copper; Or the mixture of iron, copper and activated carbon catalyst.
2, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 1 is characterized in that: between described aerobic treatment step and precipitation process step, have reflow step; And/or between described anaerobic treatment step and aerobic treatment step, has reflow step.
3, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 2 is characterized in that: in described reflow step, processed waste water is 100-400% from the aerobic treatment pond to the reflux ratio in anaerobic treatment pond; Mud is 50-200% from the precipitation process pond to the reflux ratio that aerobic treating pond refluxes.
4, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 1 and 2 is characterized in that: in described redox reaction, the iron concentration in the waste water in the described anaerobic pond remains on 5-50mg/L.
5, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 1 and 2 is characterized in that: the making method of described activated carbon catalyst may further comprise the steps:
1) with activated carbon 10%NaOH solution soaking, filtration, is washed till neutrality with deionized water;
2) soak, filter with the HCl dissolving of 1:1 again, be washed till neutrality with deionized water, dry in baking oven;
3) with above-mentioned substance at the Cu of 0.2～0.4mol/L (NO
3)
2Stir in the solution, drip 20% NaHCO
3Precipitation agent gets copper-containing substance; Or above-mentioned substance is placed the FeCl of 0.05～2.5mol/L
3Stir in the solution, get iron compound;
4) with described copper-containing substance or iron compound respectively through slaking, filtration, separate out with deionized water rinsing to non-metallic ion, be put in the baking oven dry; Obtain the copper-loaded solid of activated carbon of modification or the activated carbon of modification and carry the iron solid;
5) activated carbon of copper-loaded solid of the activated carbon of described modification or modification is carried the iron solid and activate respectively, make described activated carbon catalyst, i.e. the activated carbon of copper-loaded catalyzer of the activated carbon of modification or modification carries iron catalyst.
6, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 1 and 2 is characterized in that the filling mass ratio of the filler in the described reactor is: iron: copper: activated carbon catalyst=100%:0%～50%:0%～15%.
7, the method for processing organic industrial effluent by catalytic reduction bio-ferric technique according to claim 1 and 2 is characterized in that: the porosity of described filler is 30%～70%.
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| CN102363549A (en) * | 2011-06-30 | 2012-02-29 | 上海明诺环境科技有限公司 | Deep treatment system of membraneless industrial organic wastewater |
| CN102515426A (en) * | 2011-12-07 | 2012-06-27 | 浙江省环境保护科学设计研究院 | Anaerobic hydrolysis system for treating biorefractory waste water and anaerobic hydrolysis technology adopting the anaerobic hydrolysis system |
| CN102795705A (en) * | 2012-08-03 | 2012-11-28 | 东华工程科技股份有限公司 | Advanced bio-treatment technology for waste water |
| CN104016547A (en) * | 2014-06-19 | 2014-09-03 | 中冶建筑研究总院有限公司 | Advanced treatment and zero emission process for coking wastewater |
| CN104016548A (en) * | 2014-06-19 | 2014-09-03 | 中冶建筑研究总院有限公司 | Biochemical treatment process of coking wastewater |
| CN105481091A (en) * | 2015-12-12 | 2016-04-13 | 常州大学 | Method for treating chemical wastewater |
| CN106348546A (en) * | 2016-11-08 | 2017-01-25 | 河南君和环保科技有限公司 | Integrated processing process for waste water generated during coproduction of epoxypropane and methyl tertiary butyl ether |
| CN107522375A (en) * | 2017-08-22 | 2017-12-29 | 华南理工大学 | A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase |
| CN109161564A (en) * | 2018-09-03 | 2019-01-08 | 北京高能时代环境技术股份有限公司 | A kind of matrix liner and its preparation method and application for organic waste anaerobic dry fermentation |
| CN110981044A (en) * | 2019-12-27 | 2020-04-10 | 上海世渊环保科技有限公司 | Catalytic reduction reactor for wastewater pretreatment, wastewater pretreatment system and process thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102363549A (en) * | 2011-06-30 | 2012-02-29 | 上海明诺环境科技有限公司 | Deep treatment system of membraneless industrial organic wastewater |
| CN102515426A (en) * | 2011-12-07 | 2012-06-27 | 浙江省环境保护科学设计研究院 | Anaerobic hydrolysis system for treating biorefractory waste water and anaerobic hydrolysis technology adopting the anaerobic hydrolysis system |
| CN102795705A (en) * | 2012-08-03 | 2012-11-28 | 东华工程科技股份有限公司 | Advanced bio-treatment technology for waste water |
| CN104016547A (en) * | 2014-06-19 | 2014-09-03 | 中冶建筑研究总院有限公司 | Advanced treatment and zero emission process for coking wastewater |
| CN104016548A (en) * | 2014-06-19 | 2014-09-03 | 中冶建筑研究总院有限公司 | Biochemical treatment process of coking wastewater |
| CN104016547B (en) * | 2014-06-19 | 2016-01-20 | 中冶建筑研究总院有限公司 | A kind of coking waste water deep treatment zero-emission process |
| CN104016548B (en) * | 2014-06-19 | 2016-04-06 | 中冶建筑研究总院有限公司 | A kind of Biochemical Process for Treating Coke Plant Wastewater |
| CN105481091A (en) * | 2015-12-12 | 2016-04-13 | 常州大学 | Method for treating chemical wastewater |
| CN106348546A (en) * | 2016-11-08 | 2017-01-25 | 河南君和环保科技有限公司 | Integrated processing process for waste water generated during coproduction of epoxypropane and methyl tertiary butyl ether |
| CN107522375A (en) * | 2017-08-22 | 2017-12-29 | 华南理工大学 | A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase |
| CN109161564A (en) * | 2018-09-03 | 2019-01-08 | 北京高能时代环境技术股份有限公司 | A kind of matrix liner and its preparation method and application for organic waste anaerobic dry fermentation |
| CN110981044A (en) * | 2019-12-27 | 2020-04-10 | 上海世渊环保科技有限公司 | Catalytic reduction reactor for wastewater pretreatment, wastewater pretreatment system and process thereof |
| CN115583761A (en) * | 2022-10-31 | 2023-01-10 | 西安建筑科技大学 | Cross-flow biological filter system and nitrogen and phosphorus removal method |
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