CN104291526B - A kind of epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance - Google Patents
A kind of epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance Download PDFInfo
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- CN104291526B CN104291526B CN201410521176.1A CN201410521176A CN104291526B CN 104291526 B CN104291526 B CN 104291526B CN 201410521176 A CN201410521176 A CN 201410521176A CN 104291526 B CN104291526 B CN 104291526B
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Abstract
The invention discloses a kind of epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance, comprise: the pH value of controlling epoxy plasticizer production wastewater is 2～5, add ferrous sulfate, be heated to temperature >=70 DEG C, when stopping heating, add biochemical sludge, after reaction finishes, reaction system liquid is cooled to below 50 DEG C, by plate and frame filter press, waste water is carried out to press filtration, obtain mud after treatment; The addition of described ferrous sulfate is 0.05～0.09% of epoxy plasticizer production wastewater gross weight. The present invention is by the improvement to waste water treatment process condition, and compared with traditional epoxy plasticizer Wastewater Pretreatment, required interpolation ferrous sulfate amount reduces, and is about originally 1/10th, and sludge creation amount is few. Compared with filter cake after traditional biochemical sludge press filtration, the biochemical sludge after disposal methods of the present invention, under same filter press condition, after press filtration, the moisture content of filter cake declines more than 30%.
Description
Technical field
The invention belongs to technical field of waste water processing, specifically relate to one and can improve biochemical sludge performanceEpoxy plasticizer method of wastewater treatment.
Background technology
In epoxy plasticizer production wastewater, contain a large amount of hydrogen peroxide and grease, therefore it is being given birth toChange before processing and need to carry out pretreatment, domestic the pretreatment containing hydrogen peroxide organic wastewater is adopted conventionallyFenton oxidizing process, adds ferrous sulfate to react with hydrogen peroxide, both can remove hydrogen peroxide, can produce againThe raw hydroxyl radical free radical oxidation of organic compounds with strong oxidizing property.
Existing report for the plasticizer waste water processing that contains hydrogen peroxide also has: publication number isThe patent documentation of CN102936074A discloses a kind of pretreatment side of epoxy plasticiser factory effluentMethod, concrete steps are: the first step: epoxy plasticiser factory effluent is carried out after Production Wastewater By Combined Acidification And Demulsification, firstCarry out micro-pore aeration oil removing, then skim grease with full-automatic Oil scraper, with sodium carbonate by pH value of waste waterBe adjusted to 4.5～5.5; Second step: will pump into air-floating apparatus through first step waste water after treatment and carry out gasFloating processing, the operating order of addition of ingredients of air-floating apparatus is: first add aluminium polychloride, then add alkali lyePH value is adjusted to 7.5～8.5, finally add again PAMA, the going out of air-floating apparatusWater quartz sand filtration; The 3rd step: by the mode with bottom in and top out through second step waste water after treatmentBy filling up the filter tank of natural manganese sand, to remove hydrogen peroxide residual in waste water, obtain pretreatedEpoxy plasticiser factory effluent. This preprocess method is all mixed plasticizer waste water of processing, and gives upWater kind difference, hydrogen peroxide content is also different, is therefore difficult to ensure reach in composite waste desirable energyEnough hydrogen peroxide contents of processing. And require to ensure hydrogen peroxide content foot in waste water before entering manganese sandfiltration potEnough low (< 0.2%), otherwise hydrogen peroxide very obstinate, the loss of manganese sand is serious.
Publication number is that the patent documentation of CN103265148A discloses a kind of epoxy plasticizer production wastewaterProcessing method, the method comprises the following steps: (1) first passes into epoxy plasticizer production wastewaterIn oil interceptor, carry out oil removal processing; (2) and then by waste water pass in Fenton pond, Fenton contains in pondHaving weight is the ferrous sulfate of waste water weight 0.1%-0.4%, carries out Fenton's reaction 1-5h; (3) add againEntering lime regulates pH value to 8-9; (4) then add flocculant, flocculant consumption is waste water weight10ppm-30ppm; (5) after treating that precipitation completely, supernatant liquor is directly squeezed into biochemical system and enterRow is processed; (6) lower sediment is carried out to press filtration by plate and frame filter press, filtrate is carried out department of biochemistry equallySystem is processed. In the method, the ferrous sulfate amount of use is more; And applicant tests discovery,Make to adopt the ferrous sulfate of waste water weight 0.1%-0.4%, colleague adopts the same condition of the document,After residual peroxide in the waste water that obtains more, cannot be up to standard.
In addition, plasticizer waste water produces a large amount of excess sludges after biochemical treatment, conventionally biochemical sludge warpSludge digestion and concentrated after, after plate and frame filter press press filtration moisture content still up to more than 80%, Gao HanWater rate mud causes very large trouble in transfer and follow-up burning disposal.
Summary of the invention
The invention provides a kind of epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance,In the process of epoxy plasticizer Wastewater Pretreatment, biochemical sludge is processed simultaneously, reduced sulfuric acid AsiaWhen iron consumption, reduce the moisture content in filter cake after biochemical sludge press filtration, played mud decrementObject.
The epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance, comprising: control loopThe pH value of oxygen plasticizer production wastewater is 2～5, adds ferrous sulfate, is heated to temperature >=70 DEG C,Stopping heating time adds biochemical sludge, after reaction finishes, by reaction system liquid be cooled to 50 DEG C withUnder, by plate and frame filter press, waste water is carried out to press filtration, obtain mud after treatment;
The addition of described ferrous sulfate be 0.05 of epoxy plasticizer production wastewater gross weight～0.09％。
The addition of described biochemical sludge is 15～25% of epoxy plasticizer production wastewater cumulative volume,More preferably 20%.
Time needs that mud of the present invention adds are strict to be controlled, add too early or spend evening and affect FentonOxidation reaction, sludge disintegration reaction is not thorough.
In the present invention, described epoxy plasticizer production wastewater can adopt the production of multiple epoxy plasticizerWaste water, as preferably, described epoxy plasticizer production wastewater is that epoxy aliphatic acid methyl ester plasticizer is rawProduce waste water; In described epoxy plasticizer production wastewater the mass percentage content of hydrogen peroxide be 2～3%, more preferably 2.5%; The pH value of described epoxy plasticizer production wastewater is 3～4.
Described ferrous sulfate generally refers to ferrous sulfate heptahydrate; More preferably epoxy of its addition0.05～0.06% of plasticizer production wastewater gross weight, more preferably 0.06%. Further fallThe consumption of low ferrous sulfate, reduces sludge yield.
In this reaction system, hydrogen peroxide reacts with ferrous sulfate needs certain triggering temperature, works as reactionWhen liquid level starts to occur obvious bubble rolling in still, stop heating. For reaction of the present invention, whenWhile joining more than 70 DEG C, can meet reaction needed, hydrogen peroxide reacts and belongs to heat release with ferrous sulfateReaction, utilizes reaction heat to maintain the required temperature of this reaction in reactor. Further preferably add hot temperatureDegree is 70～80 DEG C, and the security that has further improved follow-up Fenton oxidation reaction, is suitable for industryChange and produce. Heating process can adopt Steam Heating or other mode of heatings.
When stopping heating, add biochemical sludge, biochemical sludge moisture content is about 99%. For twoThe waste water reaction that oxygen water quality degree is 2.5% 2～3 hours, hydrogen peroxide content in waste water≤0.05% can think that Fenton reaction finishes, and by condensed water coil pipe, reactor is carried out to cooling processing,Be down to below 50 DEG C when reactor temperature, by plate and frame filter press, waste water carried out to press filtration, press filtration is pressedPower is not less than 4MPa; More preferably 4～10MPa.
Biochemical sludge is the product after sewage disposal, is a kind of by organic relic, bacterium thalline, inorganicThe extremely complicated heterogeneous body of the composition such as particle, glue, the present invention is locating by Fenton oxidation reactionIn reason plasticizer production wastewater when hydrogen peroxide, hydrogen peroxide react with ferrous sulfate generation hydroxyl oneselfCan destroy biochemical sludge bacterial extracellular polymer thing by base, extracellular polymeric main component is to have hydrophilyThe polymer substance such as polysaccharide, protein with viscosity. Under the effect of Fenton reagent, born of the same parents are poly-outwardCompound is cracked, and increases the inorganicization degree of mud granule, thereby improves the dehydration property of mud, is convenient toThe flocculation sediment of mud, ensure to adopt in the inventive method sludge filter cake after treatment moisture content lower than40％。
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) the present invention is by the improvement to waste water treatment process condition, with traditional epoxy plasticizerWastewater Pretreatment is compared, and required interpolation ferrous sulfate amount reduces, be about original 1/10th, mudGeneration is few.
(2) compared with filter cake after traditional biochemical sludge press filtration, through processing method of the present invention placeBiochemical sludge after reason, under same filter press condition, after press filtration, the moisture content of filter cake declinesMore than 30%.
Brief description of the drawings
Fig. 1 is the stream of the epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance of the present inventionCheng Tu.
Detailed description of the invention
The epoxy plasticizer production wastewater adopting in embodiment can adopt applicant self Endogenous to produceObtain epoxy aliphatic acid methyl ester plasticizer production wastewater, also can adopt the epoxy aliphatic acid methyl ester of outsourcing to increaseMould the factory effluent of agent. As shown in Figure 1, detailed process is referring to embodiment 1-3 for course of reaction.
Embodiment 1
In epoxy plasticizer production wastewater, the mass percentage content of hydrogen peroxide is 2.5% left and right, pH valueBe 3～4, above-mentioned epoxy plasticizer waste water be promoted to pump to effectively to utilize volume be 15m3ReactionStill, adds and accounts for wastewater quality than the ferrous sulfate heptahydrate that is 0.06%, uses Steam Heating reactor, withShi Kaiqi reactor stirs. Be heated to approximately 75 DEG C, in reactor, liquid level starts to occur that obvious bubble turns overRoll, stop heating, add wastewater volume than the biochemical sludge that is 20%, biochemical sludge moisture content simultaneouslyBe about 99%. React 2.5 hours, hydrogen peroxide content≤0.05% in waste water (can adopt potassium permanganateMethod is monitored) can think that Fenton reaction finishes, and carries out cold by condensed water coil pipe to reactorBut process, be down to below 50 DEG C when reactor temperature, by plate and frame filter press, waste water is carried out to press filtration,Press filtration pressure is not less than 4MPa (approximately 5～6MPa).
Open filter plate, filtrate is measured to moisture content, moisture with the filtrate of the direct press filtration of biochemical sludgeRate is compared. From testing result, untreated biochemical sludge is directly adopted to same conditionPress filtration, the water content of the filter cake obtaining is 85%; And utilize after above-described embodiment 1 disposal methodsWaste water carry out press filtration, the water content of filter cake is 45%, well below containing in filter cake in prior artThe water yield.
Embodiment 2
In epoxy plasticizer production wastewater, the mass percentage content of hydrogen peroxide is 2.5% left and right, pH valueBe 3～4, above-mentioned epoxy plasticizer waste water be promoted to pump to effectively to utilize volume be 15m3ReactionStill, adds and accounts for wastewater quality than the ferrous sulfate heptahydrate that is 0.08%, uses Steam Heating reactor, withShi Kaiqi reactor stirs. Be heated to approximately 70 DEG C, in reactor, liquid level starts to occur that obvious bubble turns overRoll, stop heating, add wastewater volume than the biochemical sludge that is 20%, biochemical sludge moisture content simultaneouslyBe about 99%. React 2.5 hours, hydrogen peroxide content≤0.05% in waste water (can adopt potassium permanganateMethod is monitored) can think that Fenton reaction finishes, and carries out cold by condensed water coil pipe to reactorBut process, be down to below 50 DEG C when reactor temperature, by plate and frame filter press, waste water is carried out to press filtration,Press filtration pressure is not less than 4MPa (approximately 4～5MPa).
Open filter plate, filtrate is measured to moisture content, moisture with the filtrate of the direct press filtration of biochemical sludgeRate is compared. From testing result, untreated biochemical sludge is directly adopted to same conditionPress filtration, the water content of the filter cake obtaining is 85%; And utilize after above-described embodiment 1 disposal methodsWaste water carry out press filtration, the water content of filter cake is 40%, well below containing in filter cake in prior artThe water yield.
Embodiment 3
In epoxy plasticizer production wastewater, the mass percentage content of hydrogen peroxide is 2.5% left and right, pH valueBe 3～4, above-mentioned epoxy plasticizer waste water be promoted to pump to effectively to utilize volume be 15m3ReactionStill, adds and accounts for wastewater quality than the ferrous sulfate heptahydrate that is 0.06%, uses Steam Heating reactor, withShi Kaiqi reactor stirs. Be heated to approximately 80 DEG C, in reactor, liquid level starts to occur that obvious bubble turns overRoll, stop heating, add wastewater volume than the biochemical sludge that is 20%, biochemical sludge moisture content simultaneouslyBe about 99%. React 2 hours, hydrogen peroxide content≤0.05% in waste water (can adopt permanganimetric methodMonitor) can think that Fenton reaction finishes, and carries out cooling by condensed water coil pipe to reactorProcess, be down to below 50 DEG C when reactor temperature, by plate and frame filter press, waste water is carried out to press filtration,Press filtration pressure is not less than 4MPa (approximately 5～6MPa).
Open filter plate, filtrate is measured to moisture content, moisture with the filtrate of the direct press filtration of biochemical sludgeRate is compared. From testing result, untreated biochemical sludge is directly adopted to same conditionPress filtration, the water content of the filter cake obtaining is 85%; And utilize after above-described embodiment 1 disposal methodsWaste water carry out press filtration, the water content of filter cake is 50%, well below containing in filter cake in prior artThe water yield.
Claims (4)
1. the epoxy plasticizer method of wastewater treatment that can improve biochemical sludge performance, comprising: controlThe pH value of epoxy plasticizer production wastewater processed is 3～4, adds ferrous sulfate, be heated to temperature >=70 DEG C, when stopping heating, add biochemical sludge, after reaction finishes, reaction system liquid is cooled toBelow 50 DEG C, waste water is carried out to press filtration, obtain mud after treatment;
The addition of described ferrous sulfate be 0.05 of epoxy plasticizer production wastewater gross weight～0.06％；
In described epoxy plasticizer production wastewater, the mass percentage content of hydrogen peroxide is 2～3%;
The addition of described biochemical sludge is 15～25% of epoxy plasticizer production wastewater cumulative volume.
2. the epoxy plasticizer waste water place that can improve biochemical sludge performance according to claim 1Reason method, is characterized in that, described epoxy plasticizer production wastewater is epoxy aliphatic acid methyl ester plasticisingAgent production waste water.
3. the epoxy plasticizer waste water place that can improve biochemical sludge performance according to claim 1Reason method, is characterized in that, being heated to temperature is 70～80 DEG C.
4. the epoxy plasticizer waste water place that can improve biochemical sludge performance according to claim 1Reason method, is characterized in that, press filtration adopts plate compression, and press filtration pressure is not less than 4MPa.
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| CN1911830A (en) * | 2006-08-30 | 2007-02-14 | 华东理工大学 | Waste water treatment method for circulation use of oxidation reaction catalyst |
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| CN102491551A (en) * | 2011-11-22 | 2012-06-13 | 浙江嘉澳环保科技股份有限公司 | Treatment method for hydrogen peroxide-containing organic wastewater |
| CN102936074A (en) * | 2012-12-03 | 2013-02-20 | 浙江嘉澳环保科技股份有限公司 | Pretreatment method of epoxy type plasticizer production wastewater |
| CN103214044A (en) * | 2012-01-18 | 2013-07-24 | 中国石油化工股份有限公司 | Method for improving biodegradability of waste water produced by caprolactam ammoximation |
| CN103265148A (en) * | 2013-06-07 | 2013-08-28 | 文建方 | Method for treating wastewater in epoxy plasticizer production |
| CN103342439A (en) * | 2013-06-19 | 2013-10-09 | 江苏卡特新能源有限公司 | Treatment process for epoxy wastewater |
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Patent Citations (7)
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| CN1911830A (en) * | 2006-08-30 | 2007-02-14 | 华东理工大学 | Waste water treatment method for circulation use of oxidation reaction catalyst |
| CN101659483A (en) * | 2008-08-29 | 2010-03-03 | 中国石油化工股份有限公司 | Method for treating high-concentrated non-degradable wastewater by using wastewater containing hydrogen peroxide |
| CN102491551A (en) * | 2011-11-22 | 2012-06-13 | 浙江嘉澳环保科技股份有限公司 | Treatment method for hydrogen peroxide-containing organic wastewater |
| CN103214044A (en) * | 2012-01-18 | 2013-07-24 | 中国石油化工股份有限公司 | Method for improving biodegradability of waste water produced by caprolactam ammoximation |
| CN102936074A (en) * | 2012-12-03 | 2013-02-20 | 浙江嘉澳环保科技股份有限公司 | Pretreatment method of epoxy type plasticizer production wastewater |
| CN103265148A (en) * | 2013-06-07 | 2013-08-28 | 文建方 | Method for treating wastewater in epoxy plasticizer production |
| CN103342439A (en) * | 2013-06-19 | 2013-10-09 | 江苏卡特新能源有限公司 | Treatment process for epoxy wastewater |
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