CN105174547A - Treatment method of organic waste water - Google Patents
Treatment method of organic waste water Download PDFInfo
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- CN105174547A CN105174547A CN201510621279.XA CN201510621279A CN105174547A CN 105174547 A CN105174547 A CN 105174547A CN 201510621279 A CN201510621279 A CN 201510621279A CN 105174547 A CN105174547 A CN 105174547A
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Abstract
The invention discloses a treatment method of organic waste water. The treatment method of the organic waste water comprises the following steps that 1, on the condition that the pressure ranges from 1 MPa to 8 MPa, the temperature ranges from 150 DEG C to 280 DEG C, and a catalyst exists, wet oxidation is conducted on the organic waste water, and after a reaction is finished, filtration is conducted to obtain filtrate I; 2, precipitator is added to the filtrate I, a reaction is conducted under the alkaline condition, and filtrate III is obtained after the reaction is finished and filtration is conducted; 3, adsorbent is added to the filtrate III, and treatment effluent is obtained through stirring and filtration; the organic waste water adopts benzenesulfonic acid organic waste water and/or benzoic acid organic waste water. The treatment method of the organic waste water is easy to operate, and the removal rate of organic waste water COD is high; the treatment method of the organic waste water is suitable for the continuous treatment of industrial organic waste water and prone to being applied and popularized in the industry.
Description
Technical field
The invention belongs to treatment of Organic Wastewater field, be specifically related to a kind for the treatment of process of organic waste water.
Background technology
Phenylsulfonic acid and benzoic acid derivative are important fine chemicals, are the important intermediate preparing phenolic compound, dyestuff, medicine, foodstuff additive, leather retanning agent and agrochemical.Phenylsulfonic acid class and benzoic acid derivative have very high mobility in water surrounding, easily cause water pollution.The water-soluble height of Phenylsulfonic acid compounds, polarity are strong, biological degradation difficulty is large; Adopt the more difficult Phenylsulfonic acid class of method or the benzoic acids organic waste waters such as general flocculation, extraction and absorption method.How efficiently process Phenylsulfonic acid class or benzoic acids organic waste water are the emphasis of research at present.
The treatment process of existing Phenylsulfonic acid class organic waste water mainly contains advanced oxidation processes, complexing abstraction, emulsion liquid membrane extraction and resin adsorption method etc.Advanced oxidation processes can make the structural transformation of compound, reduces COD and TOC of waste water, improves B/C value.Advanced oxidation processes mainly comprises Fenton reagent oxidation style, Ozonation and wet oxidation process.
Wet oxidation process is a kind of method that can process high density, difficult degradation, poisonous and hazardous organic waste water, usually needs to carry out at higher temperature (125 ~ 300 DEG C) and larger pressure (0.5 ~ 20MPa).The introducing of catalyzer and the stronger oxygenant of oxidation capacity improves this method, and reaction is carried out under comparatively gentle condition.If catalytic wet hydrogen peroxide oxidation (CWPO) method is the OH utilizing hydrogen peroxide to decompose a large amount of strong oxidizing properties of generation in reaction process, by OH, organism exhaustive oxidation is become final product CO
2and H
2o or be converted into innoxious substance.
Publication number is that the Chinese patent literature of CN1289725A discloses one complexometric extraction para Toluic Acid pretreatment method for wastewater, adopt complexing agent, solubility promoter, thinner mixed solvent at normal temperatures para Toluic Acid's waste water carry out multi-stage solvent extraction, until the biochemical oxygen demand value of extraction raffinate reaches emission standard.Solvent cost of the present invention is high, long processing period, and processing environment is more severe.
Publication number is a kind of method that the Chinese patent literature of CN100999355A discloses catalytic wet air oxidation degradating m-nitrobenzene sodium sulfonate, that the m-nitrobenzene sodium sulfonate solution with certain TOC concentration is added volume is in the reactor of 1L, then hydrogen peroxide and oxygen is added successively as oxygenant and cupric nitrate as catalyzer, sealing; Pass into the oxygen that initial oxygen pressure is 0.1 ~ 15MPa, stirring heating is warmed up to 150 ~ 300 DEG C and degrades, and cool after reaction 0.5H ~ 2.5H, the clearance measuring TOC is 96.51%.Present method processing cost is higher, and Catalytic Wet Oxidation reaction adopts hydrogen peroxide as oxygenant, and wastewater treatment process Hazard ratio is comparatively large, and the copper introduced by catalyzer easily causes secondary pollution to process water outlet.
Summary of the invention
The invention provides a kind for the treatment of process of organic waste water, the method significantly can reduce the COD value of organic waste water.
A treatment process for organic waste water, comprises the following steps:
(1) be 1 ~ 8MPa at pressure, temperature is 150 ~ 280 DEG C, under catalyzer existent condition, carries out wet oxidation to organic waste water, after reaction terminates, filters and obtains filtrate I;
(2) in filtrate I, add precipitation agent, react in the basic conditions, after reaction, filter to get filtrate II;
(3) in filtrate II, add sorbent material, agitation and filtration obtains processing water outlet;
Described organic waste water is the organic waste water of Phenylsulfonic acid class organic waste water and/or phenylformic acid and derivative thereof.
Organic waste water carries out wet oxidation reaction under catalyst, macromolecular cpd in organic waste water is made to be degraded into small molecules, again through the precipitation of step (2) and the absorption of step (3), effectively can improve the clearance of the COD of organic waste water, reduce the colourity of process water outlet.Under described wet oxidation temperature and pressure, the treatment process of integrating step (1)-step (3), the COD clearance of organic waste water is greater than 95%.
The inventive method is applicable to the process of Phenylsulfonic acid class organic waste water and/or benzoic acids organic waste water.As preferably, in described Phenylsulfonic acid class organic waste water, contain one or more of formula 1 structural compounds;
Wherein Z is-X ,-OH ,-OR
1,-COR
5,-NH
2,-NHR
2,-NR
3r
4,-NO
2or C
1-4alkyl, R
1, R
2, R
3, R
4and R
5for C
1-4alkyl; N is 0 or 1-5.
Wherein, Z is-H ,-OH ,-OR
1,-NH
2,-NHR
2,-NR
3r
4or C
1-4alkyl; N is 1-3, and the wet oxidation treatment effect that substituting group is positioned at the compound of position and/or contraposition between sulfonic acid is good.
As preferably, in described Phenylsulfonic acid class organic waste water, Phenylsulfonic acid kind compound content is 0.05-2wt%.
Wet oxidation reaction effect is subject to the impact of temperature of reaction and pressure.When wet oxidation reaction temperature is too high, reaction pressure can raise fast, and operational risk increases, and operation, capital construction cost increase.When temperature is less, the Phenylsulfonic acid compounds in organic waste water and/or the more difficult oxidation of benzoic acid derivative or oxygenolysis slow.
Reaction pressure is greater than 8MPa, and the pressure of increase is little to the contribution of reaction process, but increases the burden of reaction vessel or pipeline.Pressure is less than 1MPa, and reaction process is too slow, does not even react.
The effect of pH value during wet oxidation on wet oxidation has impact.As preferably, the pH value of wet oxidation is 2 ~ 11.PH value is too high, and wet oxidation effect is bad; PH value is too low, and equipment damage is larger.
Further preferably, the pH value of wet oxidation is 3 ~ 10.
The reaction times of wet oxidation is longer, and the effect of wet oxidation reaction can be better, but reacts very large to the infringement of equipment under long High Temperature High Pressure.In order to take into account the effect of wet oxidation, preferably, the time of wet oxidation is 1 ~ 6h.Further preferably, the time of wet oxidation is 2 ~ 4h.
In order to improve the efficiency of wet oxidation, the present invention adopts catalyzer, can ensure that COD clearance is more than 95% in wet oxidation process.
Described catalyzer is homogeneous catalyst or heterogeneous catalyst, and in the effective active component content in catalyzer, the dosage of described catalyzer is the 0.05-2.5% of organic waste water quality.
Homogeneous catalyst is water-soluble catalyzer, and heterogeneous catalyst is water-insoluble catalyzer.
As preferably, described heterogeneous catalyst is one or more in the copper of loading type, iron, noble metal catalyst.
Further preferably, described heterogeneous catalyst is Ru/C, Rh/C, Pd/C and Ru/TiO
2, Rh/TiO
2, Pd/TiO
2in one or more.
As preferably, described homogeneous catalyst is one or more in water-soluble mantoquita, manganese salt, nickel salt, cobalt salt, molysite.
Further preferably, described homogeneous catalyst is Cu (NO
3)
2, Fe (NO
3)
2, Fe (NO
3)
3, CuSO
4, CoSO
4, NiSO
4, MnSO
4in one or more.
Further preferred, described homogeneous catalyst is Cu (NO
3)
2, CoSO
4or CuSO
4.
Homogeneous catalyst can introduce cupric ion, iron ion or other ions in waste water, likely can cause secondary pollution to process water outlet, so, under the prerequisite ensureing catalytic effect, catalyst levels should be the least possible, preferably, the consumption of homogeneous catalyst is 0.05 ~ 1wt% of organic waste water quality.
In industrial production, the normal reactor adopting preparation of metals, iron material reactor is in the majority.Inevitably there is dissolved ferric iron in reaction process in reaction soln, and then cause containing iron in waste water, thus cause the salt colourity that is recovered to high.
As ammonia nitrogen (NH in waste water
3-N) content higher time, cupric ion and ammonium complexing, direct salt steaming can cause in salt aobvious blue containing cupric ion, in treatment of Organic Wastewater process, should preferentially by this kind of nonferrous metal ion as the removal of the precipitation such as cupric ion, iron ion.
As preferentially, described precipitation agent is one or more in water miscible sulfide, sulfohydrate, oxyhydroxide; The molar weight that feeds intake of described precipitation agent is that in organic waste water, catalyzer adds the 1-1.5 of molar weight doubly.
The consumption of precipitation agent, slightly larger than the theoretical charging capacity calculated according to stoichiometric ratio, can ensure the isoionic abundant removal of Cu in waste water, iron.
Further preferably, described precipitation agent is sodium sulphite, Sodium sulfhydrate or sodium hydroxide.
After adding precipitation agent, keep be no less than 30min the duration of contact of precipitation agent and organic waste water, after reaction, obtain filtrate III through suction filtration, the particles such as filtrate III CuS, FeS containing a small amount of black.Filter residue can continue to make catalyzer and reuse.In order to reduce the black particle in filtrate III further, preferably, the pH of filtrate III is adjusted to alkalescence, and then adds the sorbent materials such as gac and carry out adsorption filtration, the filtrate of gained carries out the process of step (3) again.
In order to improve the treatment effect of organic waste water, reduce the colourity that salt steams the salt reclaimed, as preferably, in step (2), first in filtrate (I), add flocculation agent, stir flocculation, filter to get filtrate (II), then in filtrate (II), add precipitation agent, described flocculation agent is one or more in ferrous sulfate, polymerization ferrous sulfate, PAFS, polymerize aluminum chloride.
After adding flocculation agent, treat that flocculation agent dissolves completely, then add liquid caustic soda and regulate pH to 8 ~ 10, keep be no less than 30min the duration of contact of flocculation agent and waste water, after flocculation, filter, obtain filtrate (II), then add precipitation agent stirring reaction, filter and obtain filtrate III; Also can add sorbent material in filtrate (II), after stirring, filter to get filtrate III.Filtrate (I) first through flocculation treatment, and then is reacted with precipitation agent, effectively can reduce the colourity of process water outlet, improve the clearance of COD.
As preferably, the consumption of flocculation agent is 0.05 ~ 1wt% of organic waste water quality.
In step (3), preferably, described sorbent material is gac, activated coke or diatomite, and the consumption of sorbent material is 0.02 ~ 1wt% of organic waste water quality.
Preferably, by pH regulator to 5 ~ 9 of filtrate III, and then add sorbent material and carry out adsorption bleaching.The adsorption time of sorbent material is no less than 30min, has adsorbed rear filtration and has obtained connecing subdiaphanous process water outlet, and the COD clearance of process water outlet can reach more than 95%.
In Industrial Wastewater Treatment, the waste liquid amount of final discharge is more few better, as preferably, also comprise step (4), the process water outlet obtained is processed to step (3) and carries out underpressure distillation, and underpressure distillation gained concentrated solution is mixed in pending organic waste water, using gained mixed solution as the organic waste water in step (1);
Step (5), circulation carries out step (1) ~ (4) 3 ~ 5 times, completes wastewater treatment.
Step provided by the invention (1) adopts operate continuously to step (5), the concentrated solution of gained is mixed with pending organic waste water, then the operation of step (1) ~ step (5) is carried out, concentrated solution does not directly discharge or enters biochemical system, but be mixed in pending organic waste water and process, solve the problem that concentrated solution can not directly discharge, reduce the quantity discharged of organic waste.But micromolecular organic acid salt and other material that can not be degraded may be assembled in concentrated solution, when carrying out circulation wet oxidation, the COD clearance of next batch waste water wet oxidation may be reduced, but, after the wet-type oxidation technology condition that the present invention adopts can ensure that concentrated solution participates in repeatedly wet oxidation, COD clearance still maintains more than 90%.
Process water outlet in the present invention after charcoal absorption can meet the demand of MVR (mechanical steam recompression technology) underpressure distillation, the salt of recyclable white, and the COD of phlegma meets in line standard.
The inventive method is applicable to the continuous treatment of waste water, is mixed by organic waste water with air or oxygen, as organic waste water mixes in gas liquid mixer with air or oxygen, obtains gas-liquid mixture.Gas-liquid mixture enters in oxidizing reactor again and carries out wet oxidation reaction after interchanger heats up, and another tube side that gained oxidation treatment liquid enters interchanger as thermal source is that follow-up organic waste water heats up, and reduces own temperature.Oxidation treatment liquid after heat exchange cooling after filtration, flocculation, must water outlet be processed after copper removal and charcoal absorption, process water outlet concentrates through MVR, and phlegma is directly recycled or directly discharged; Concentrated solution is directly back to step (1), through step (1)-step (5) re-treatment.
The present invention is also by realizing the continuous treatment of waste water with under type: organic waste water heats up through interchanger, directly enter oxidizing reactor, air or oxygen is passed into again to oxidizing reactor, increasing temperature and pressure is to required reaction conditions, oxidation treatment liquid is obtained after reaction terminates, another tube side that gained oxidation treatment liquid enters interchanger as heating agent is that follow-up organic waste water heats up, and reduces own temperature.Oxidation treatment liquid after heat exchange cooling after filtration, flocculation, must water outlet be processed after copper removal and charcoal absorption, process water outlet concentrates through MVR, and phlegma is recycled or directly discharged; Concentrated solution is directly back to step (1), through step (1)-step (5) re-treatment.
The inventive method is equally applicable to the process of benzoic acids organic waste water, as preferably, contains one or more of formula 2 structural compounds in described benzoic acids organic waste water;
Wherein Y is-X ,-OH ,-OR
6,-COR
7,-NH
2,-NHR
8,-NR
9r
10,-NO
2or C
1-4alkyl, R
6, R
7, R
8, R
9and R
10for C
1-4alkyl; N is 0 or 1-5.
As preferably, a kind for the treatment of process of benzoic acids organic waste water, comprises the following steps:
(1) be 2-11 at pH, pressure is 1 ~ 8MPa, and temperature is 180 ~ 260 DEG C, and under catalyzer existent condition, para Toluic Acid's class organic waste water carries out wet oxidation, after reaction terminates, filters and obtains filtrate I; The consumption of catalyzer is 0.05 ~ 1wt% of benzoic acids organic waste water quality; The time of wet oxidation is 1 ~ 4h; Described catalyzer is water-soluble mantoquita.
(2) in filtrate I, add flocculation agent, and regulate pH to flocculate, flocculation is filtered, obtains filtrate II; The consumption of described flocculation agent is 0.05 ~ 1wt% of benzoic acids organic waste water quality;
(3) in filtrate II, add sulfide or sulfohydrate, then suction filtration obtains filtrate III; The consumption of described sulfide or sulfohydrate is that in benzoic acids organic waste water, catalyzer adds the 1-1.5 of molar weight doubly;
(4) in filtrate III, add sorbent material, filter and obtain processing water outlet; Described sorbent material is gac or diatomite, and the consumption of sorbent material is 0.02 ~ 1wt% of benzoic acids organic waste water quality.
Organic waste water containing formula 1 and formula 2 structural compounds is also applicable to the inventive method.
The treatment process of organic waste water provided by the invention is simple to operate, and the clearance of organic waste water COD is high; And be suitable for the continuous treatment of industrial organic waste water, be easy to industrially apply.
Embodiment
Embodiment 1
The present embodiment adopts the sulfonated waste water (3 produced in Disperse Blue-60 production process, 4-dichloro benzosulfonic acid waste water), with sulfonated waste water quality for benchmark, containing 3 of 4wt% in waste water, the sodium sulfate of 4-dichloro benzosulfonic acid, 5wt%, the sodium-chlor of 0.9wt%, COD=27900mg/L, pH=4.
(1) in sulfonated waste water, add NaOH solid regulate pH=7, add the CuSO that massfraction is 0.5%
45H
2o, as catalyzer (with sulfonated waste water quality for benchmark), reacts 3h under temperature 240 DEG C, pressure 5MPa condition, and reaction terminates rear separation and obtains red filtrate (i.e. filtrate I).
(2) in filtrate I, the FeSO that massfraction is 0.5% is added
47H
2o (with sulfonated waste water quality for benchmark), treats FeSO
47H
2after O dissolves completely, add the liquid caustic soda adjustment pH=8.5 that massfraction is 30%, flocculation 30min, filters and obtains blue filtrate II.
(3) in filtrate II, the Na that massfraction is 0.6% is added
2s9H
2o (with sulfonated waste water quality for benchmark), then add 0.1% waste active carbon, reaction 30min, filter and obtain filtrate III for black, the filter residue obtained can be used as catalyzer and reuses).
(4) in filtrate III, add vitriol oil readjustment pH=6.0, adding massfraction is that 0.2% gac (with sulfonated waste water quality for benchmark) adsorbs 30min, obtain subdiaphanous process water outlet, COD is 1200mg/L, COD clearance is 95.7%.
(5) water outlet underpressure distillation will be processed, phlegma COD=40mg/L; Concentrated solution is colourless, concentrated solution COD=13920mg/L.Concentrated solution is back to step (1), through step (1)-step (5) circular treatment.
Embodiment 2
The waste water of embodiment 2 is the same with the waste water of embodiment 1.
(1) in sulfonated waste water, add solid NaOH regulate pH=9, add the CuSO of 0.5wt%
45H
2o (using sulfonated waste water quality for benchmark), as catalyzer, under temperature 260 DEG C, pressure 7MPa condition, reacts 2h.Reaction terminates rear mistake and filters filter residue, obtains the treatment solution (i.e. filtrate I) of oyster.
(2) in filtrate I, add the FeSO of 0.5%
47H
2o (with sulfonated waste water quality for benchmark), treats FeSO
47H
2after O dissolves completely, add the liquid caustic soda adjustment pH=8.5 that massfraction is 30%, flocculation 30min, filters and obtains blue treatment solution, be i.e. filtrate II.
(3) in filtrate II, add NaHS (with sulfonated waste water quality for benchmark) and 0.1% waste active carbon of 0.6wt%, stirring reaction 30min removes complex copper, and the filtrate III of filtration is black (CuS can be used as catalyzer and reuses).
(4) in filtrate IV, add vitriol oil readjustment pH=6.0, the diatomite (with sulfonated waste water quality for benchmark) adding 0.2wt% adsorbs 30min, and obtain subdiaphanous pretreatment fluid, its COD=1370mg/L, clearance are 95.1%.
(5) by pretreatment fluid underpressure distillation, colourless phlegma is obtained, its COD=10.53mg/L; Concentrated solution is colourless, its COD=9707.5mg/L.
Embodiment 3
(1) original sub-block (circulation 0)
Former water is the same with the waste component of embodiment 1.
1-1, add in sulfonated waste water solid NaOH regulate pH=8, add the CuSO of 0.5wt%
45H
2o (using former quality for benchmark), as catalyzer, reacts 3h under temperature 240 DEG C, pressure 5MPa condition.Reaction terminates rear mistake and filters filter residue, and obtain the treatment solution (i.e. filtrate I) of oyster, its pH=2.1, COD=2700mg/L, clearance are 90.3%.
1-2, in filtrate I, add the FeSO of 0.5wt%
47H
2o (with former quality for benchmark), after it dissolves completely, add liquid caustic soda and regulate pH=8.5, flocculation 30min, suction filtration obtains blue treatment solution (i.e. filtrate II), its COD=2418mg/L.
1-3, in filtrate II, add the Na of 0.6wt%
2s9H
2o and 0.1% waste active carbon (with former quality for benchmark), reaction 30min removes complex copper, and the pretreatment fluid (i.e. filtrate III) of filtration is black (CuS makees the catalyzer of next circulation).
1-4, add in filtrate III dilute sulphuric acid (sulfuric acid content is 5%) readjustment pH=6.0, the gac (with former quality for benchmark) adding 0.2wt% adsorbs 30min, obtain subdiaphanous pretreatment fluid, its COD=1250mg/L, COD clearance is 95.5%.
1-5, by pretreatment fluid underpressure distillation, obtain colourless phlegma, its COD=61mg/L; Concentrated solution is colourless, its COD=12450mg/L.
(2) first time MVR concentrated solution cyclically utilizing (circulation 1)
Add solid NaOH in 2-1, Xiang Yuanshui and regulate pH=8, add the MVR concentrated solution that step 1-5 process obtains, waste water COD=23000mg/L after mixing, then adds CuS that 1-3 obtains as catalyzer, under temperature 240 DEG C, pressure 5MPa condition, reacts 3h.Reaction terminates rear mistake and filters filter residue, and obtain the treatment solution (i.e. filtrate I) of oyster, its pH=1.32, COD=2830mg/L, clearance are 87.7%.
2-2, in filtrate I, add the FeSO of 0.5wt%
47H
2o (with former water and step (1) concentrated solution total mass for benchmark), after it dissolves completely, add liquid caustic soda (massfraction is 30%) and regulate pH=8.0, flocculation 30min, after adding 0.1% charcoal absorption, suction filtration obtains blue treatment solution (i.e. filtrate III), its COD=2140mg/L.
2-3, in filtrate III, add the Na of 0.6wt%
2s9H
2o (with former water and step (1) concentrated solution total mass for benchmark), reaction 30min removes complex copper, and the pretreatment fluid (i.e. filtrate IV) of filtration is black (CuS continues to recycle).
2-4, in filtrate IV, add gac (with former water and step (1) concentrated solution total mass for the benchmark) absorption of 0.1wt%, suction filtration obtains subdiaphanous pretreatment fluid, add sulfuric acid readjustment pH=3.5 again, produce without hydrogen sulfide bubble, 0.1% charcoal absorption is again added in pretreatment fluid, filtration obtains subdiaphanous pretreatment fluid, and its COD=1380mg/L, clearance are 94.0%.
2-5, the underpressure distillation of step 2-4 gained pretreatment fluid, obtain colourless phlegma, its COD=27.09mg/L; Concentrated solution is colourless, its COD=12640mg/L.
(3) second time MVR concentrated solution cyclically utilizing (circulation 2)
3-1, Xiang Yuanshui add solid NaOH and regulate pH=8, add the MVR concentrated solution of step 2-6 gained, the waste water COD=23790mg/L after mixing, and then add CuS that 2-3 obtains as catalyzer, under temperature 240 DEG C, pressure 5MPa condition, react 3h.Reaction terminates rear suction filtration removing filter residue, obtains the treatment solution of oyster, its about pH=1.91, after adding 0.1% charcoal absorption, obtains filtrate I, COD=3300mg/L, clearance is 86.2%.
3-2, in filtrate I, add the FeSO of 0.5wt%
47H
2o (with former water and step (2) concentrated solution total mass for benchmark), after it dissolves completely, add liquid caustic soda and regulate pH=8.0, flocculation 30min, suction filtration obtains blue treatment solution (i.e. filtrate II).
3-3, in filtrate II, add the Na of 0.6wt%
2s9H
2o (with former water and step (2) concentrated solution total mass for benchmark), reaction 30min removes complex copper, and the pretreatment fluid (i.e. filtrate III) of suction filtration is black (CuS particle is less, partly enters in filtrate);
3-4, in filtrate III, add 0.1wt% gac (with former water and step (2) concentrated solution total mass for benchmark) absorption, suction filtration obtains subdiaphanous pretreatment fluid (i.e. filtrate IV), in filtrate IV, add sulfuric acid adjust about pH=4, obtain solution, produce without hydrogen sulfide bubble in the process, add 2 dropping liquid adjusting PH with base=5.5 again, survey COD=1927mg/L, clearance are 91.9%.
3-5, by step 3-4 gained solution decompression distillation and concentration, obtain colourless phlegma, its COD=24.08mg/L; Concentrated solution is colourless, its COD=14220mg/L.
(4) third time MVR concentrated solution cyclically utilizing (circulation 3)
4-1, Xiang Yuanshui add solid NaOH and regulate pH=8, add the MVR concentrated solution of step 3-5 gained, mix rear COD=32030mg/L, then add the CuSO of 0.5wt%
45H
2o (using former water and step (3) concentrated solution total mass for benchmark) is as catalyzer, 3h is reacted under temperature 240 DEG C, pressure 5MPa condition, reaction terminates rear suction filtration removing filter residue, obtain the treatment solution (i.e. filtrate I) of oyster, its pH=1.5, COD=4900mg/L, clearance are 84.7%.
4-2, in filtrate I, add the FeSO of 0.5wt%
47H
2o (with former water and step (3) concentrated solution total mass for benchmark), after it dissolves completely, adds liquid caustic soda and regulates pH=8.0, flocculation 30min, add 0.1% gac suction filtration and obtain blue treatment solution (i.e. filtrate II).
4-3, in filtrate II, add the Na of 0.8wt%
2s9H
2o (with former water and step (3) concentrated solution total mass for benchmark) reacts 30min and removes complex copper, add 0.1% gac suction filtration and obtain subdiaphanous pretreatment fluid, add the vitriol oil again and adjust about pH=3.5, produce without hydrogen sulfide bubble, liquid feeding adjusting PH with base=8.2 again, then add the Na of 0.65g
2s9H
2o, produces without precipitation, adjusts pH=2.5 adularescent turbid material.
4-4, gac (with former water and step (3) concentrated solution total mass for the benchmark) suction filtration adding 0.2wt% obtain colourless transparent solution, liquid feeding adjusting PH with base=6.1, survey COD=3000mg/L, clearance is 90.6%.
4-5, step 4-4 gained solution decompression to be distilled, concentrated, obtain colourless phlegma and concentrated solution.
(5) the 4th MVR concentrated solution cyclically utilizing (circulation 4)
Xiang Yuanshui adds solid NaOH and regulates pH=8, adds step 4-5 gained MVR concentrated solution, mixes rear COD=35070mg/L, then add the CuSO of 0.5wt%
45H
2o (using former water and step (4) concentrated solution total mass for benchmark), as catalyzer, reacts 4h under temperature 240 DEG C, pressure 5MPa condition.Reaction terminates rear suction filtration removing filter residue, obtains treatment solution azury, its pH=1
Left and right, COD=5003mg/L, clearance are 81.9%.
The COD removal effect of step (1) ~ (5) gained as shown.
Table 1
As shown in Table 1, along with the increase of MVR concentrated solution cyclically utilizing number of times, COD total removal rate after the clearance of wet oxidation and charcoal absorption has decline in various degree, this may be that material owing to can not degrade in wet oxidation causes at system internal recycle, extend the time of wet oxidation, the clearance of wet oxidation can be improved.
Embodiment 4
Segregation waste water in Isosorbide-5-Nitrae-dihydroxyanthraquinone production process, the organic waste that mainly contains in waste water is phthalic acid, COD=63710mg/L, pH=1.
(1) in hydrolyzed waste water, add solid NaOH regulate pH=9, add the CuSO of 0.5wt%
45H
2o (using wastewater quality of emanating for benchmark), as catalyzer, under temperature 200 DEG C, pressure 3MPa condition, reacts 4h.Reaction terminates rear suction filtration removing filter residue, and obtain the treatment solution (i.e. filtrate I) of oyster, its about pH=4.0, COD=4100mg/L, clearance are 93.4%.
(2) in filtrate I, add the FeSO of 0.5wt%
47H
2o (with wastewater quality of emanating for benchmark), treats FeSO
47H
2after O dissolves completely, add the liquid caustic soda adjustment pH=8.5 that massfraction is 3.2%, flocculation 30min, suction filtration obtains blue treatment solution, i.e. filtrate II, its COD=3296mg/L.
(3) in filtrate II, add the NaHS (with wastewater quality of emanating for benchmark) of 0.5wt%, reaction 30min removes complex copper, and the filtrate III of suction filtration is black.
(4) in filtrate III, add vitriol oil readjustment pH=6.0, add 0.2wt% gac (with hydrolyzed waste water quality for benchmark) and adsorb 30min, obtain subdiaphanous treatment solution, its COD=2328mg/L, clearance are 96.4%.
(5) by pretreatment fluid underpressure distillation, colourless phlegma is obtained, its COD=10.53mg/L; Concentrated solution is colourless, its COD=9707.5mg/L, and concentrated solution is back to step (1) and next batch waste water processes together.
Embodiment 5
Asccharin factory effluent is brown troubled liquor; Containing methyl alcohol, toluene, benzene, anthranilic acid, 0-chloro-benzoic acid, Phenylsulfonic acid and carboxylate methyl ester thereof etc.; COD is 23460mg/L; Cu in waste water
2+concentration be 118.6mg/L.
(1) in asccharin factory effluent, add NaOH solid regulate pH=8, add the CuSO that massfraction is 0.2wt%
45H
2o (using asccharin factory effluent quality for benchmark), as catalyzer, reacts 3h under temperature 220 DEG C, pressure 4MPa condition, and reaction terminates the filtrate (i.e. filtrate I) that rear suction filtration obtains oyster.
(2) in filtrate I, the FeSO that massfraction is 0.5wt% is added
47H
2o (with asccharin factory effluent quality for benchmark), treats FeSO
47H
2after O dissolves completely, add liquid caustic soda and regulate pH=8.5, flocculation 30min, suction filtration obtains blue filtrate II.
(3) in filtrate II, the Na that massfraction is 0.35wt% is added
2s9H
2o (with asccharin factory effluent quality for benchmark), reaction 30min, suction filtration obtains filtrate III for black.
(4) in filtrate III, add vitriol oil readjustment pH=6.0, adding massfraction is that 0.2wt% gac (with asccharin factory effluent quality for benchmark) adsorbs 30min, obtain subdiaphanous process water outlet, COD is 490mg/L, COD clearance is 95.3%.
(5) water outlet underpressure distillation will be processed, phlegma COD=21mg/L; Concentrated solution is colourless, concentrated solution COD=1392mg/L.Concentrated solution is back to step (1), through step (1)-step (5) circular treatment.
Embodiment 6
Be that with embodiment 4 difference removal step (2) adds the NaHS copper removal of 0.5wt% in filtrate II.Add 0.2% gac and the decolouring of 0.2% diatomite adsorption in the waste water after copper removal after, obtain almost colourless treatment solution, its COD=3028mg/L, clearance are 95%.Compare with embodiment 4, without flocculation treatment, the COD clearance of final process process declines to some extent.
Embodiment 7
Compare with embodiment 1, difference is, step (1) adopts Ru/C to replace CuSO
45H
2o is as catalyzer.After process terminates, record the COD=2483mg/L of process water outlet, COD clearance is 91.1%.
Comparative example 1
Be with embodiment 1 difference, in step (1), do not add to CuSO
45H
2o.After process terminates, record the COD=9000mg/L of process water outlet, COD clearance is 67.7%.
Comparative example 2
Compare with embodiment 1, difference is, in step (1), temperature of reaction is 300 DEG C, pressure 10MPa, and after process terminates, record the COD=2539mg/L of process water outlet, COD clearance is 90.9%.Compare with embodiment 1, increase the temperature and pressure of wet oxidation reaction, the COD of process water outlet declines on the contrary to some extent.
Claims (10)
1. a treatment process for organic waste water, is characterized in that, comprises the following steps:
(1) be 1 ~ 8MPa at pressure, temperature is 150 ~ 280 DEG C, carries out Catalytic Wet Oxidation to organic waste water, after reaction terminates, filters and obtains filtrate I;
(2) in filtrate I, add precipitation agent, react in the basic conditions, after reaction, filter to get filtrate II;
(3) in filtrate II, add sorbent material, agitation and filtration obtains processing water outlet;
Described organic waste water is the organic waste water of Phenylsulfonic acid class organic waste water and/or phenylformic acid and derivative thereof.
2. the treatment process of organic waste water as claimed in claim 1, it is characterized in that, described catalyzer is homogeneous catalyst or heterogeneous catalyst, and in the effective active component content in catalyzer, the dosage of described catalyzer is the 0.05-2.5% of organic waste water quality.
3. the treatment process of organic waste water as claimed in claim 2, it is characterized in that, described homogeneous catalyst is one or more in water-soluble mantoquita, manganese salt, nickel salt, cobalt salt, molysite.
4. the treatment process of organic waste water as claimed in claim 1, is characterized in that, described heterogeneous catalyst is one or more in the copper of loading type, iron, noble metal catalyst.
5. the treatment process of organic waste water as claimed in claim 1, it is characterized in that, in step (2), first in filtrate (I), add flocculation agent, stir flocculation, filter to get filtrate (II), then in filtrate (II), adds precipitation agent, and described flocculation agent is one or more in ferrous sulfate, polymerization ferrous sulfate, PAFS, polymerize aluminum chloride.
6. the treatment process of the organic waste water as described in claim 2 or 5, is characterized in that, described precipitation agent is one or more in water miscible sulfide, sulfohydrate, oxyhydroxide; The molar weight that feeds intake of described precipitation agent is that in organic waste water, catalyzer adds the 1-1.5 of molar weight doubly.
7. the treatment process of organic waste water as claimed in claim 1, it is characterized in that, described sorbent material is gac, activated coke or diatomite, and the consumption of sorbent material is 0.02 ~ 1wt% of organic waste water quality.
8. the treatment process of organic waste water as claimed in claim 1, it is characterized in that, also comprise step (4), the process water outlet obtained is processed to step (3) and carries out underpressure distillation, and underpressure distillation gained concentrated solution is mixed in pending organic waste water, using gained mixed solution as the organic waste water in step (1);
Step (5), circulation carries out step (1) ~ (4) 3 ~ 5 times, completes wastewater treatment.
9. the treatment process of organic waste water as claimed in claim 1, is characterized in that, contains formula 1 structural compounds one or more in described Phenylsulfonic acid class organic waste water;
Wherein Z is-X ,-OH ,-OR
1,-COR
5,-NH
2,-NHR
2,-NR
3r
4,-NO
2or C
1-4alkyl, R
1, R
2, R
3, R
4and R
5for C
1-4alkyl; N is 0 or 1-5.
10. the treatment process of organic waste water as claimed in claim 1, is characterized in that, contains formula 2 structural compounds one or more in described benzoic acids organic waste water;
Wherein Y is-X ,-OH ,-OR
6,-COR
7,-NH
2,-NHR
8,-NR
9r
10,-NO
2or C
1-4alkyl, R
6, R
7, R
8, R
9and R
10for C
1-4alkyl; N is 0 or 1-5.
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