CN105084600A - Method for efficiently treating salt-containing organic wastewater and application of method - Google Patents

Method for efficiently treating salt-containing organic wastewater and application of method Download PDF

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CN105084600A
CN105084600A CN201510541441.7A CN201510541441A CN105084600A CN 105084600 A CN105084600 A CN 105084600A CN 201510541441 A CN201510541441 A CN 201510541441A CN 105084600 A CN105084600 A CN 105084600A
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salt
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waste water
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CN105084600B (en
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张云保
徐雷金
胡启木
张静
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Extraordinary Splendour Environmental Science And Technology Co Ltd In Zhejiang
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Extraordinary Splendour Environmental Science And Technology Co Ltd In Zhejiang
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Abstract

The invention discloses a method for efficiently treating salt-containing organic wastewater and application of the method. The method comprises the following steps: (1) filtering the salt-containing organic wastewater, and performing diffusion dialysis on obtained filtrate to obtain acid solution or alkaline solution and salt-containing organic matter solution; (2) treating the salt-containing organic solution by utilizing a bipolar membrane to obtain organic matter-containing solution, acid solution and alkaline solution; (3) performing wet oxidation on the organic matter-containing solution to obtain treatment liquid; (4) performing aftertreatment on the treatment liquid to obtain water. According to the method for efficiently treating the salt-containing organic wastewater, disclosed by the invention, not only can the COD (chemical oxygen demand) value of the wastewater be obviously reduced but also matter in the wastewater can be effectively recycled.

Description

A kind of method of efficient process salt-containing organic wastewater and application thereof
Technical field
The present invention relates to technical field of waste water processing, be specifically related to a kind of method and application thereof of efficient process salt-containing organic wastewater.
Background technology
In chemical process, inevitably producing various salt-containing organic wastewater, in order to meet the demand of protection of the environment, needing to process these waste water, to reach emission standard.
Sulpho Tobias Acid, having another name called aniline-2,5-disulfonic acid (2-is amino to benzene disulfonic acid), is a kind of dyestuff intermediate, mainly for the manufacture of direct fast blue RGL, activity Yincui blue KGL, reactive brilliant yellow and reactive orange, white dyes etc.Containing acid about 28% in Sulpho Tobias Acid waste water, sodium chloride-containing about 10%, adopts existing method of wastewater treatment, effectively can not recycle acid wherein.
G salt is white, needle-shaped crystals, G salt produce need through oversulfonate, saltout, suction strainer three process, wherein sulfonation is the secondary sulfonation reaction that ethyl naphthol and sulfuric acid, nicotinic acid carry out, after the sulfonation of G salt, the ethyl naphthol of about 64% is only had to change G acid into, still have the sulfonaphthol of more than 30% to be trapped in G salt waste water, wherein main isomer is R acid.Make G acid become to salt out by salting-out method, and R acid and other by product are still stayed in G salt waste water.G salt is separated by suction filtration with G salt waste water, and G salt waste water is sap green, acidity, saliferous, coloured, high density, therefore, needs to be processed G salt waste water.
K acid, i.e. 2-naphthalene ammonia-3,6,8-trisulfonic acid is a kind of important fine-chemical intermediate, is mainly used in the production of azo active dyestuff, matching stain and the pigment dyestuffs such as such as reactive golden yellow K-RAZ, reactive yellow M-5R, reactive brilliant orange K-7R.
The production technique of current 2-naphthalene ammonia-3,6,8-trisulfonic acid be with beta naphthal be raw material through a sulfonation, saltout, ammonia solution, segregation, secondary sulfonation, washing, filtration, the process such as drying obtain.K acid waste water has following feature:
(1) acid strong, pH is 0.2 ~ 0.6;
(2) colourity is dark, and waste water is brown, and colourity is about 5000 times;
(3) Pollutant levels are high, and COD is 2000 ~ 3500mg/L, and wherein main component is 2-naphthalene ammonia-3,6,8-trisulfonic acid, and content is 1500 ~ 3000mg/L, also contain the inorganic salt such as the sodium sulfate of about 1.5% in addition;
(4) be difficult to biological degradation, because 2-naphthalene ammonia-3,6,8-trisulfonic acid has stable naphthalene ring, play the sulfonate functional base of passivation in molecule containing three, molecular structure is very stable, biodegradability extreme difference simultaneously, is difficult to adopt biochemical method degraded;
(5) toxicity is large, and 2-naphthalene ammonia-3,6,8-trisulfonic acid belongs to condensed-nuclei aromatics, and the amino group containing intoxicating in molecule, there is strong bio-toxicity, if without suitably process directly discharge, by serious pollution of water environment, be detrimental to health.
Bromamine acid, has another name called 1-amino-4-bromo anthraquinone-2-sulfonic acid, is mainly used in dyestuff intermediate.Production method many employings 1-aminoanthraquinone of bromamine acid is raw material, oleum sulfonation is used in vitriol oil medium, and then by oleum bromine bromination in vitriol oil medium, obtain through steps such as diluting, neutralize, be refining, in production process, produce a large amount of waste water.
The mode of existing process trade effluent is varied, is reduced the pollutant load in waste water by various physical chemistry and biological means, and such as, the treatment process of existing H acid segregation waste water is: first, extracts H acid segregation waste water; Then, carry out concentrated salt steaming, the sodium sulfate obtained does fixed-end forces or reuse.Due to the excess production capacity of sodium sulfate, and the cost that concentrated salt steams is high, the sodium sulfate salt inferior quality of acquisition, and range of application is narrow.
Diffusion dialysis as a kind of take concentration difference as the membrane separation technique of impellent, utilize translucent or perm-selective ion-exchange membrane that the solute in solution is moved to lower concentration side by film by high density side.Due to its have simple to operate, energy consumption is low, non-secondary pollution, easily and the advantage such as other technique coupling, be widely used in the field of various generation spent acid alkali.
The core of diffusion dialysis is: 1, the concentration difference of ion-exchange membrane both sides solution; 2, the selective penetrated property of ion-exchange membrane.Divide according to the kind of ion-exchange membrane, anion-exchange membrane diffusion dialysis and cationic exchange membrane diffusion dialysis can be divided into.Anion-exchange membrane diffusion dialysis is mainly used to the acid in recovered acid salt mixture, and cationic exchange membrane diffusion dialysis is mainly used to reclaim the alkali in alkali salt mixture.
Bipolar membrane electrodialysis is the electrodialysis that Bipolar Membrane and one pole film are differently combined to form, and is dissociated by common electrodialytic salt to combine with the dissociating of water molecules of Bipolar Membrane, makes the H that in solution, corresponding salt ion and Bipolar Membrane water decomposition produce +and OH -in conjunction with being converted into corresponding bronsted lowry acids and bases bronsted lowry.On the membrane stack of same Bipolar Membrane, inorganic salt and organic salt can be converted into corresponding bronsted lowry acids and bases bronsted lowry.
Nowadays in a lot of chemical processs, owing to often using neutralization reaction, create a large amount of brine wastes, the salt in brine waste can be changed into corresponding bronsted lowry acids and bases bronsted lowry by bipolar membrane electrodialysis, the bronsted lowry acids and bases bronsted lowry that recovery obtains can be used for the neutralization reaction of Chemical Manufacture simultaneously.
Summary of the invention
The invention provides a kind of method of efficient process salt-containing organic wastewater, significantly can not only reduce the COD value of waste water, can also the material in waste water effectively be recycled.Meanwhile, utilize method of the present invention, can improve the production technique of part organic products, realize cleaner production.
A method for efficient process salt-containing organic wastewater, comprises the following steps:
(1) filter the organic wastewater of saliferous, gained filtrate, through diffusion dialysis, obtains the organic solution of acidic solution or basic solution and saliferous;
(2) utilize the organic solution of Bipolar Membrane to saliferous to process, obtain containing organic solution, and acidic solution and basic solution;
(3) carry out wet oxidation to containing organic solution, obtain treatment solution;
(4) aftertreatment is carried out to treatment solution, obtain water outlet.
Method provided by the invention is applicable to the organic wastewater of all kinds of saliferous, comprises the acid waste water of saliferous and the alkaline waste water of saliferous.Such as, Sulpho Tobias Acid sour water, K acid waste water, G salt waste water, bromamine acid waste water, T acid waste water, H acid waste water etc.
Method provided by the invention can adopt industrial continuous prodution, and namely the organic wastewater of saliferous experiences the treating processes of step (1) ~ step (4) successively continuously, obtains standard compliant relief liquor.
First method provided by the invention filters trade effluent (i.e. the organic wastewater of saliferous), to remove suspended substance and iron, calcium, the solid matters such as magnesium, then semipermeable partition or perm-selective ion-exchange membrane is utilized to the selection of filtrate through effect, filtrate is separated into the organic solution of acidic solution and saliferous, in acidic solution direct reuse to corresponding workshop section, the organic solution of saliferous then utilizes Bipolar Membrane to be further separated, obtain acidic solution and basic solution, and containing organic solution, containing organic soln using wet oxidation, be small molecules by organic matter degradation, discoloring agent is finally utilized to remove substance that show color, complete the process of waste water.
As preferably, the reaction conditions of diffusion dialysis in step (1): adopt anion-exchange membrane to carry out diffusion dialysis to the acid waste water of saliferous, adopts cationic exchange membrane to carry out diffusion dialysis to the alkaline waste water of saliferous.
As preferably, the reaction conditions of Bipolar Membrane in step (2): individual membrane voltage <2.5V, current density 100 ~ 600A/m 2, temperature is 1 ~ 40 DEG C, and electrode solution adopts massfraction to be the metabisulfite solution of 1% ~ 5%.
The object of wet oxidation is the organic matter degradation in solution to be small molecules, reduce COD value, because the condition of wet oxidation is more harsh, use for a long time, inevitably equipment is caused damage, in order to take into account the effect of wet oxidation, preferably, the reaction conditions of wet oxidation in step (3): pH is 2 ~ 12, and pressure is 2 ~ 8MPa, temperature is 180 ~ 300 DEG C, and the reaction times is 2 ~ 6h.
Further preferably, the reaction conditions of wet oxidation in step (3): pH is 4 ~ 9, and pressure is 2 ~ 6MPa, and temperature is 230 ~ 270 DEG C, and the reaction times is 3 ~ 5h.
Preferred again, the reaction conditions of wet oxidation in step (3): pH is 7 ~ 8, and pressure is 2 ~ 4MPa, and temperature is 250 ~ 270 DEG C, and the reaction times is 3 ~ 5h.
After wet oxidation, COD value significantly reduces, and obtaining needs in treatment solution to carry out aftertreatment further, obtains water outlet, described aftertreatment can for adding discoloring agent removing substance that show color, in order to reach desirable decolorizing effect, preferably, sorbent material is adopted to carry out aftertreatment to treatment solution in step (4).
Carry out aftertreatment according to sorbent material to treatment solution, the add-on of sorbent material is 0.05 ~ 0.5% for the treatment of solution quality, stirring reaction 20 ~ 60min.
Present invention also offers a kind of production technique of Sulpho Tobias Acid of improvement, bisnaphthol successively through oversulfonate, neutralization, distillation, ammonification, acidifying, TOBIAS ACID 97MIN.& 98MIN. sulfonation, be hydrolyzed, saltout, wash and obtain Sulpho Tobias Acid, successively after filtration and diffusion dialysis, the sulfuric acid reuse obtained is to acid out workshop section for the waste water that Sulpho Tobias Acid produces.
Containing massfraction in Sulpho Tobias Acid waste water is the sulfuric acid of about 28%, and massfraction is the sodium-chlor of about 10%, method provided by the invention is adopted to process Sulpho Tobias Acid waste water, can effective recycling sulfuric acid, improve the utilization ratio of raw material.
Acidic substance in handled solution all can be separated by the diffusion dialysis in the present invention and Bipolar Membrane, and reuse is in required workshop section again, namely achieves the effective recycling of component in waste water, again saves the resources of production.
The present invention compared with prior art, has following beneficial effect:
(1) treatment process provided by the invention significantly can reduce the COD value in waste water, and the clearance of COD is more than 96%;
(2) treatment process provided by the invention adopts diffusion dialysis and Bipolar Membrane process to waste water, in the bronsted lowry acids and bases bronsted lowry reuse obtained to corresponding production workshop section, improves the utilization ratio of raw material.
(3) treatment process provided by the invention is suitable for continuous prodution, is easy to industrially apply.
Embodiment
Embodiment 1
H acid waste water, in black, COD=26030mg/L, pH=2.
(1) filter: H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(2) diffusion dialysis: utilize anion-exchange membrane diffusion dialysis to process filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous, the rate of recovery 90% of sulfuric acid.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 10%, and in basic solution, the massfraction of sodium hydroxide is 4%, and the massfraction of ammonia is 4%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2.5V, current density is 600A/m 2, temperature is 30 DEG C, and electrode solution adopts massfraction to be the metabisulfite solution of 5%.
(4) wet oxidation: the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 2h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2083mg/L, NH 3-N=164.2mg/L.
(5) adsorb: the still waste water that goes out of step (4) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.2% (to regulate the quality of the waste water after pH for benchmark), the micro-yellow filtrate obtained, add gac (to regulate the quality of the waste water after pH for benchmark) the whip attachment 30min that massfraction is 0.3% again, suction filtration obtains transparent processing liquid, COD=150mg/L, saltiness 4%.
Embodiment 2
H acid waste water, in black, COD=26030mg/L, pH=2.
(1) filter: H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(2) diffusion dialysis: utilize anion-exchange membrane diffusion dialysis to process filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 9%, and in basic solution, the massfraction of sodium hydroxide is 3.9%, and the massfraction of ammonia is 3.5%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 400A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(4) wet oxidation: the pH regulator to 8 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 1.5h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2483mg/L, NH 3-N=165.0mg/L.
(5) adsorb: go out in still waste water to add in step (4) gac (to go out the quality of still waste water for benchmark) the whip attachment 30min that massfraction is 0.3%, suction filtration obtains yellowish treatment solution, its COD=1545mg/L.
Embodiment 3
H acid waste water, in black, COD=130000mg/L, pH=1.
(1) filter: H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(2) diffusion dialysis: utilize anion-exchange membrane diffusion dialysis to process filtrate, through diffusion dialysis effect, obtains the organic solution of sulfuric acid and saliferous.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 11%, and in basic solution, the massfraction of sodium hydroxide is 4.5%, and the massfraction of ammonia is 4.5%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2.5V, current density is 600A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(4) wet oxidation: by the pH regulator 7 containing organic solution obtained after Bipolar Membrane process, then add in autoclave, pass into the air of 30atm, in 250 DEG C of reactions cooling after a hour;
Pressure release after cooling, then the air continuing to pass into 30atm continues in 250 DEG C of reactions cooling after a hour;
After cooling pressure release, then pass into the air of 30atm, react 1.5 hours at 250 DEG C.Water outlet is yellow, COD=6500mg/L, COD clearance 95%.
(5) decolour: in the water outlet of step (4), add massfraction is 0.3% gac (with the effluent characteristics of step (4) for benchmark), filter after whip attachment 30min, adding massfraction is again suction filtration after the charcoal absorption of 0.1%, filtrate is light yellow, surveys about COD=6000mg/L.
Comparative example 1
Be that step (5) adopts ClO with the difference of embodiment 3 2decolouring, concrete operations are as follows:
The ClO of 0.2% is added in the water outlet of step (4) 2(ClO 2consumption with the effluent characteristics of step (4) for benchmark), 30min is reacted under normal temperature, add again massfraction be 0.1% gac (with the effluent characteristics of step (4) for benchmark) adsorb suction filtration after 30min, color is safran, and decolorizing effect is undesirable.
Comparative example 2
Be that step (5) adopts Fe/C to decolour with the difference of embodiment 3, concrete operations are as follows:
The water outlet pH=4 of pacing rapid (4), to add massfraction be 0.2% gac and massfraction is filter after 2% iron powder (with the effluent characteristics of step (4) for benchmark) reacts 4h, be adjusted to pH=8 again, suction filtration after flocculation 30min, filtrate is safran, and decolorizing effect is undesirable.
Embodiment 4
(1) refined naphthalene successively through sulfonation, nitrated, neutralization, reduction, T acid segregation, alkali fusion, H acid emanate prepare H acid.
(2) filter: H acid segregation waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(3) diffusion dialysis: utilize anion-exchange membrane diffusion dialysis to process filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous.
(4) Bipolar Membrane process: utilize the saliferous organic solution that Bipolar Membrane treatment step (3) obtains, obtain basic solution and massfraction is the sulfuric acid of 9.8%, in basic solution, the massfraction of sodium hydroxide is 3.7%, and the massfraction of ammonia is 3.7%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 450A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
By this step gained sulfuric acid reuse to H acid segregation workshop section, steaming is revolved to gained basic solution, obtains sodium hydroxide reuse to alkaline melt workshop section.
(5) wet oxidation: by the pH regulator to 7 containing organic solution obtained after step (4) Bipolar Membrane process, then squeeze in wet oxidation still, be warming up to 250 DEG C, pressure 6MPa, lower the temperature after passing into atmospheric oxidation 1.5h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2107mg/L.
(6) adsorb: go out in still waste water to add in step (5) gac (with step (4) go out still wastewater quality for benchmark) the whip attachment 30min that massfraction is 0.2%, suction filtration obtains flaxen treatment solution, then pH to 6.0 is regulated, color becomes yellow, add gac (with step (4) go out still wastewater quality for benchmark) the whip attachment 30min that massfraction is 0.3% again, suction filtration obtains yellowish treatment solution, its COD=1487mg/L.
(7) filter: T acid segregation waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(8) diffusion dialysis: utilize anion-exchange membrane diffusion dialysis to process step (7) gained filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous.
(9) Bipolar Membrane process: the saliferous organic solution utilizing Bipolar Membrane treatment step (8), obtains basic solution and massfraction is the sulfuric acid of 9.8%, by sulfuric acid reuse to T acid segregation workshop section.
The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 450A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(10) wet oxidation: by the pH regulator to 8 containing organic solution obtained after step (9) Bipolar Membrane process, add the CuSO that massfraction is 0.5% 45H 2o is as catalyzer (with T acid segregation wastewater quality for benchmark), 3h is reacted under temperature 260 DEG C, pressure 7MPa condition, reaction terminates the filtrate (i.e. filtrate I) that rear suction filtration obtains oyster, and its about pH=2.1, COD clearance are 85%.
(11) in filtrate I, the FeSO that massfraction is 0.5% is added 47H 2o (with T acid segregation wastewater quality for benchmark), treats FeSO 47H 2after O dissolves completely, add the liquid caustic soda adjustment pH=8.5 that massfraction is 5.5%, flocculation 30min, suction filtration obtains blue filtrate II.
(12) in filtrate II, the Na that massfraction is 0.6% is added 2s9H 2o (with T acid segregation wastewater quality for benchmark), reaction 30min, removing complex copper, suction filtration obtains filtrate III for black (CuS particle is less, and part enters in filtrate).
(13) in filtrate III, add the vitriol oil readjustment pH=6.0 that massfraction is 0.6%, adding massfraction is that 0.2% gac (with T acid segregation wastewater quality for benchmark) adsorbs 30min, obtain subdiaphanous filtrate, its COD clearance is 96%.
Embodiment 5
(1) TOBIAS ACID 97MIN.& 98MIN. prepares Sulpho Tobias Acid through sulfonation, acid out, press filtration successively;
(2) filter: Sulpho Tobias Acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(3) diffusion dialysis: utilize anionresin EDBM to process step (2) gained filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous.
(4) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 10%, and in basic solution, the massfraction of sodium hydroxide is 4%, and the massfraction of ammonia is 4%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 500A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(5) wet oxidation: the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 2h.The COD clearance recording out still waste water is 96%.
(6) adsorb: the still waste water that goes out of step (5) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.5% (to regulate the quality of the waste water after pH for benchmark), the filtrate obtained is almost colourless transparent, COD=150mg/L, saltiness 8%.
Embodiment 6
G salt waste water, in black, COD=49500mg/L, pH=1.
(1) G salt waste water is filtered, to remove the insoluble substance such as suspended substance and iron, calcium, magnesium in waste water.
(2) utilize anionresin EDBM to process filtrate, dialysis obtains the organic solution of sulfuric acid and saliferous, the rate of recovery 92% of sulfuric acid.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 10%, and in basic solution, the massfraction of sodium hydroxide is 4%, and the massfraction of ammonia is 3.8%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 600A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(4) wet oxidation: the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 2h.
Record out still wastewater pH=4.5, COD=3156mg/L, NH 3-N=215mg/L.
(5) adsorb: the still waste water that goes out of step (4) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.5% (to regulate the quality of the waste water after pH for benchmark), the filtrate obtained is almost colourless transparent, COD=596mg/L, saltiness 5%.
Embodiment 7
Bromamine acid waste water, in black, COD=37659mg/L, pH=1.5.
(1) bromamine acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(2) utilize semi-permeable membranes to process filtrate, through diffusion dialysis effect, obtain the organic solution of sulfuric acid and saliferous, the rate of recovery 90% of sulfuric acid.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 11%, and in basic solution, the massfraction of sodium hydroxide is 4.2%, and the massfraction of ammonia is 3.9%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 500A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(4) wet oxidation: the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 2h.
Record out still wastewater pH=4.5, COD=3286mg/L, NH 3-N=164.2mg/L.
(5) adsorb: the still waste water that goes out of step (4) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.5% (to regulate the quality of the waste water after pH for benchmark), the filtrate obtained is almost colourless transparent, COD=980mg/L, saltiness 4.1%.
Embodiment 8
K acid waste water, in black, COD=20030mg/L, pH=2.
(1) K acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium.
(2) utilize semi-permeable membranes to process filtrate, through diffusion dialysis effect, obtain the organic solution of sulfuric acid and saliferous, the rate of recovery 91% of sulfuric acid.
(3) Bipolar Membrane process: the organic solution utilizing Bipolar Membrane process saliferous, obtains basic solution and massfraction is the sulfuric acid of 9.8%, and in basic solution, the massfraction of sodium hydroxide is 3.9%, and the massfraction of ammonia is 3.7%.The reaction conditions of Bipolar Membrane: individual membrane voltage is 2V, current density is 450A/m 2, temperature is 30 DEG C, and electrode solution adopts the metabisulfite solution of 5%.
(4) wet oxidation: the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeezes in wet oxidation still, is warming up to 250 DEG C, pressure 6MPa, lowers the temperature after passing into atmospheric oxidation 2h.
Record out still wastewater pH=4.5, COD=1956mg/L, NH 3-N=158mg/L.
(5) adsorb: the still waste water that goes out of step (4) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.4% (to regulate the quality of the waste water after pH for benchmark), the filtrate obtained is almost colourless transparent, COD=358mg/L, saltiness 3.7%.

Claims (7)

1. a method for efficient process salt-containing organic wastewater, is characterized in that, comprise the following steps:
(1) filter the organic wastewater of saliferous, gained filtrate, through diffusion dialysis, obtains the organic solution of acidic solution or basic solution and saliferous;
(2) utilize the organic solution of Bipolar Membrane to saliferous to process, obtain containing organic solution, and acidic solution and basic solution;
(3) carry out wet oxidation to containing organic solution, obtain treatment solution;
(4) aftertreatment is carried out to treatment solution, obtain water outlet.
2. the method for efficient process salt-containing organic wastewater as claimed in claim 1, it is characterized in that, the reaction conditions of diffusion dialysis in step (1): adopt anion-exchange membrane to carry out diffusion dialysis to the acid waste water of saliferous, adopts cationic exchange membrane to carry out diffusion dialysis to the alkaline waste water of saliferous.
3. the method for efficient process salt-containing organic wastewater as claimed in claim 1, is characterized in that, the reaction conditions of Bipolar Membrane in step (2): individual membrane voltage <2.5V, current density 100 ~ 600A/m 2, temperature is 1 ~ 40 DEG C, and electrode solution adopts massfraction to be the metabisulfite solution of 1% ~ 5%.
4. the method for efficient process salt-containing organic wastewater as claimed in claim 1, is characterized in that, the reaction conditions of wet oxidation in step (3): pH is 2 ~ 12, and pressure is 2 ~ 8MPa, and temperature is 180 ~ 300 DEG C, and the reaction times is 2 ~ 6h.
5. the method for efficient process salt-containing organic wastewater as claimed in claim 1, is characterized in that, adopt sorbent material to carry out aftertreatment to treatment solution in step (4).
6. the method for efficient process salt-containing organic wastewater as claimed in claim 1, it is characterized in that, carry out aftertreatment according to sorbent material to treatment solution, the add-on of sorbent material is 0.05 ~ 0.5% for the treatment of solution quality, stirring reaction 20 ~ 60min.
7. the production technique of the Sulpho Tobias Acid improved, bisnaphthol successively through oversulfonate, neutralization, distillation, ammonification, acidifying, TOBIAS ACID 97MIN.& 98MIN. sulfonation, be hydrolyzed, saltout, wash and obtain Sulpho Tobias Acid, it is characterized in that, successively after filtration and diffusion dialysis, the sulfuric acid reuse obtained is to acid out workshop section for the waste water that Sulpho Tobias Acid produces.
CN201510541441.7A 2015-08-28 2015-08-28 A kind of method and its application of efficient process salt-containing organic wastewater Active CN105084600B (en)

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CN105566176A (en) * 2015-11-26 2016-05-11 浙江奇彩环境科技股份有限公司 Improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid production process
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CN105645644A (en) * 2016-01-07 2016-06-08 浙江蓝极膜技术有限公司 Technique for recovering sulfuric acid from sulfuric acid/sodium sulfate-containing wastewater by two-stage diffusion dialysis, two-stage electrodialysis and bipolar membrane
CN105668889A (en) * 2016-01-07 2016-06-15 浙江蓝极膜技术有限公司 Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method
CN105645644B (en) * 2016-01-07 2018-06-08 浙江蓝极膜技术有限公司 A kind of technique for recycling sulfuric acid in sulfur acid and sodium sulfate wastewater with two sections of diffusion dialysis, two sections of electrodialysis and Bipolar Membrane
CN106865706A (en) * 2017-03-14 2017-06-20 湖北科林博伦新材料有限公司 A kind of toluene oxidation method prepares the treatment and circulation utilization method in phenmethylol technique containing organic matter salt solution
CN109502707A (en) * 2018-11-13 2019-03-22 浙江工业大学 One kind containing H2SO4, DMSO, tetrabutyl ammonium sulfate waste water processing method

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