CN105565566A - Method for performing Fenton treatment on 6-nitro-1-diazo-2-naphthol-4-sulfonic acid wastewater and coproducing sodium sulfate - Google Patents
Method for performing Fenton treatment on 6-nitro-1-diazo-2-naphthol-4-sulfonic acid wastewater and coproducing sodium sulfate Download PDFInfo
- Publication number
- CN105565566A CN105565566A CN201510940078.6A CN201510940078A CN105565566A CN 105565566 A CN105565566 A CN 105565566A CN 201510940078 A CN201510940078 A CN 201510940078A CN 105565566 A CN105565566 A CN 105565566A
- Authority
- CN
- China
- Prior art keywords
- nitro
- waste water
- sodium sulfate
- sulfonic acid
- fenton process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 29
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 29
- 238000011282 treatment Methods 0.000 title abstract description 9
- ARAINKADEARZLZ-ZHACJKMWSA-N 4,4,5,5-tetramethyl-2-[(e)-2-phenylethenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1\C=C\C1=CC=CC=C1 ARAINKADEARZLZ-ZHACJKMWSA-N 0.000 title abstract 3
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000017105 transposition Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- ZRRGOUHITGRLBA-UHFFFAOYSA-N stattic Chemical compound [O-][N+](=O)C1=CC=C2C=CS(=O)(=O)C2=C1 ZRRGOUHITGRLBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000010786 composite waste Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract 1
- 235000011128 aluminium sulphate Nutrition 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KSTGSVANFMJGGB-UHFFFAOYSA-N 2-ethylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CC)=CC=C21 KSTGSVANFMJGGB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for performing Fenton treatment on 6-nitro-1-diazo-2-naphthol-4-sulfonic acid wastewater and coproducing sodium sulfate, which comprises the following steps: (1) adding alkali into 6-nitro-1-diazo-2-naphthol-4-sulfonic acid wastewater, and regulating the pH value to 2.0-3.0; (2) under stirring conditions, adding activated carbon, FeSO4 and H2O2 into the wastewater subjected to pH value regulation to perform oxidation reaction; (3) adding alkali into the oxidated wastewater to regulate the pH value to 9-10; (4) adding an Al2(SO4)3 solution into the wastewater treated by the step (3) until the pH value of the reaction system reaches 6-7, sufficiently standing and settling to obtain a turbid solution, and filtering the turbid solution to obtain a filtrate; (5) if the filtrate obtained in the step (4) satisfies the treatment requirements, concentrating by evaporation and drying to obtain the industrial-grade sodium sulfate; and if the filtrate obtained in the step (4) does not satisfy the treatment requirements, repeating the steps (2)-(4) until the filtrate satisfies the treatment requirements. The treatment method has the advantages of simple technique and no environment pollution, and can coproduce sodium sulfate in the treatment process, thereby maximally utilizing the resources.
Description
Technical field
The invention belongs to Industrial Wastewater Treatment and the reuse technology field of environment protection, be specifically related to the waste water comprehensive treating process produced in 6-nitro-1,2,4-sulfonic acid production process, co-producing sodium sulfate, belongs to cleaner production category simultaneously.
Background technology
6-nitro-1,2,4-sulfonic acid, No. CAS is 5366-84-7, and structure is as shown in formula I, and Chinese another name is 6-nitro-DNSA, a kind of important dyestuff intermediate, mainly for the manufacture of matching stain and metallized dye.
The production method of 6-nitro-1,2,4-sulfonic acid take ethyl naphthol as main raw material, prepares through nitrosification, sulfonation, reduction transposition, diazotization, acid out, the operation such as nitrated.Waste water in production process mainly contains three sources: (1) reduction transposition; (2) acid out; (3) nitrated, wherein nitration waste water can reuse in sulfonation and acid out.The waste water main component that reduction transposition and acid out produce is naphthalene derivative, it forms complexity, containing gas chromatography, acidity is 5 ~ 8%, salinity is 8 ~ 15, colourity is 15000 ~ 35000 times, and COD is 10000 ~ 20000mg/L, belongs to the organic waste water of high density, highly acidity, high salinity, dark shade, difficult degradation.
The method of current this type of waste water of process mainly contains two kinds: (1) complexing abstraction, complexometric extraction process has high efficiency, highly selective, but due to the impurity in extraction and back-extraction process add up, repeatedly after circular treatment, extraction efficiency reduces, and strip liquor is difficult simultaneously.(2) traditional Fenton facture, traditional Fenton oxidation technology is mainly through neutralizing excessive acid with lime, produce the precipitations such as calcium sulfate, Adsorption organism, although percent of decolourization > 90% can be realized, but organic clearance lower (COD clearance is about 60%-70%), and H
2o
2the lower processing cost that causes of utilization ratio is high, because of oxygenizement thoroughly final outflow water be that brown color to brown is difficult to make discharged wastewater met the national standard, more difficultly reach reuse requirement, and produce a large amount of solid waste, raising enterprise production cost, impacts environment.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of method of Fenton process 6-nitro-1,2,4-sulfonic acid co-production sodium sulfate, the method technique is simple, free from environmental pollution, simultaneously can co-producing sodium sulfate in process, reaches resource maximum using.
A method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate, comprises the following steps:
(1) in 6-nitro-1,2,4-sulfonic acid waste water, add alkali and regulate its pH value to 2.0 ~ 3.0;
(2) in the waste water mixing up pH value, gac, FeSO is added under stirring
4and H
2o
2carry out oxidizing reaction;
(3) in the waste water after oxidation, add alkali and regulate its pH to 9 ~ 10;
(4) Al is added in the waste water processed to step (3) under stirring
2(SO
4)
3solution, until reaction system pH to 6 ~ 7, sufficient standing sedimentation obtains turbid liquid, filters obtain filtrate to this turbid liquid;
(5) if the filtrate that step (4) obtains reaches processing requirements, then technical grade sodium sulfate is obtained after evaporation concentration, drying; If the filtrate that step (4) obtains does not reach processing requirements, then repeating step (2) ~ (4), until reach processing requirements.
As preferably, described 6-nitro-1,2,4-sulfonic acid waste water is in 6-nitro-1,2,4-sulfonic acid production process, one or both composite wastes produced in reduction transposition or acid out step.Described 6-nitro-1,2,4-sulfonic acid is produced and referred to ethyl naphthol is main raw material, through nitrosification, sulfonation, reduction transposition, diazotization, acid out, nitrated etc. production technique.
As preferably, in step (1) and (3), alkali used is one or both in solid sodium carbonate or 25 ~ 35% aqueous sodium hydroxide solutions.
As preferably, in step (2), the FeSO added
4for solid, FeSO
4dosage is that 1 ~ 10mmol/L (refers to every 1L waste water and adds 1 ~ 10mmolFeSO
4);
The H added
2o
2mass percent concentration is 25 ~ 35%, H
2o
2dosage is 5 ~ 20ml/L.
As preferably, in step (2), gac dosage is 0.5 ~ 2g/L, at FeSO
4and H
2o
2add before.Wherein, first add gac and can make the abundant adsorb organic compound of gac, go into carbonium ion center, promote H
2o
2decompose speed and the efficiency of the hydroxyl radical free radical degradation of organic substances produced, improve H
2o
2utilization ratio.
As preferably, in step (2), temperature of reaction is 25 ~ 50 DEG C, and the reaction times is 1 ~ 2h, and reactive mode is standing.
As preferably, in step (4), the Al added
2(SO
4)
3mass percent concentration is 10 ~ 30%.
In the present invention, if filtrate does not reach requirement, then adjust ph to 2.0 ~ 3.0, repeating step (2) ~ (4), adjust ph can use sulfuric acid, also directly can use waste water, for most of waste water, the number of times of repeating step (2) ~ (4) is 2 ~ 4 times.
As preferably, as liquor C OD≤200mg/L, during colourity≤16 times, reach processing requirements, now, the sodium sulfate purity obtained is high, and waste water environmentally safe.
Compared with the method for existing Fenton process organic waste water, beneficial effect of the present invention is as follows:
(1) one or both composite wastes unification that this method will be reduced in 6-nitro-1,2,4-sulfonic acid process in transposition or acid out process processes, and improves waste water treatment efficiency and plant factor.
(2) with in solid sodium carbonate or 25 ~ 35% aqueous sodium hydroxide solutions, one or both regulate waste water, without limestone vegetation, not only can reduce the generation of solid waste, and the salinity in waste water can be made single, are convenient to recycle.
(3) at FeSO
4, H
2o
2add gac before, be convenient to charcoal absorption organism, go into chain carrier, promote H
2o
2decompose speed and the efficiency of the hydroxyl radical free radical degradation of organic substances produced, improve H
2o
2utilization ratio.
(4) gac can adsorb organism water-soluble in waste water, through sedimentation, filtration, removes together with organism mud, improves waste water treatment efficiency.And gac as flocculating aids, can improve filtering rate.
(5) with 10 ~ 30% Al
2(SO
4)
3, not only can adjust back wastewater pH, and generate flocculation agent again after adjusting pH to 6 ~ 7, the organism in waste water can be removed by sedimentation further.
(6) by continuous oxidation, sedimentation, filtration procedure 2 ~ 4 times, 6-nitro-1 can be realized, 2, the colourity of 4-acid oxysome waste water, COD efficiently remove that (chroma removal rate reaches 99.9%, COD clearance is greater than 98%), stable effluent quality, can by obtaining technical grade sodium sulfate after evaporation concentration, drying.
(7) present method is without the need to being equipped with particular device, only needs the simple operationss such as stirring, sedimentation, filtration, and treatment scheme is relatively simple, and processing costs is lower.
Embodiment
Embodiment 1
The 6-nitro-1,2,4-sulfonic acid of 200ml reduction transposition waste water is placed in beaker, adjusts pH to 2.5 with sodium carbonate, add 0.3g gac at 35 DEG C, the FeSO of 1mmol
4, and then add the H that 3ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 2h, be that 25% aqueous sodium hydroxide solution regulates pH to 10 with mass percent, under stirring, add the Al that massfraction is 10% slowly
2(SO
4)
3solution, adjusts pH to 6.2, leaves standstill 0.5h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 3 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, content reaches more than 98%.
Embodiment 2
The 6-nitro-1,2,4-sulfonic acid acid out waste water of 200ml is placed in beaker, adjusts pH to 2.0 with sodium carbonate, add 0.4g gac at 45 DEG C, the FeSO of 2mmol
4, and then add the H that 4ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 1.5h, regulate pH to 9.5 with 35% aqueous sodium hydroxide solution, under stirring, add the Al that massfraction is 30% slowly
2(SO
4)
3solution, adjusts pH to 6.5, leaves standstill 1h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 2 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, content reaches more than 98%.
Embodiment 3
The reduction transposition of the 6-nitro-1,2,4-sulfonic acid of each 100ml and acid out waste water are placed in beaker, adjust pH to 2.8 with 30% sodium hydroxide, add 0.1g gac at 25 DEG C, the FeSO of 0.5mmol
4, and then add the H that 2ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 1.5h, regulate pH to 9.3 with 30% aqueous sodium hydroxide solution, under stirring, add the Al that massfraction is 20% slowly
2(SO
4)
3solution, adjusts pH to 6.5, leaves standstill 0.5h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 4 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, content reaches more than 98%.
Embodiment 4
The 6-nitro-1,2,4-sulfonic acid acid out waste water of the reduction transposition of the 6-nitro-1,2,4-sulfonic acid of 50ml and 150ml is placed in beaker, adjusts pH to 2.3 with sodium carbonate, add 0.3g gac at 40 DEG C, the FeSO of 1.5mmol
4, and then add the H that 2ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 2h, regulate pH to 9.8 with 25% aqueous sodium hydroxide solution, under stirring, add the Al that massfraction is 30% slowly
2(SO
4)
3solution, adjusts pH to 6.3, leaves standstill 1h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 3 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, content reaches more than 98%.
Embodiment 5
The 6-nitro-1,2,4-sulfonic acid acid out waste water of the reduction transposition of the 6-nitro-1,2,4-sulfonic acid of 150ml and 50ml is placed in beaker, adjusts pH to 2.3 with sodium carbonate, add 0.2g gac at 40 DEG C, the FeSO of 2mmol
4, and then add the H that 3ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 1h, regulate pH to 9.0 with 35% aqueous sodium hydroxide solution, under stirring, add the Al that massfraction is 20% slowly
2(SO
4)
3solution, adjusts pH to 6.8, leaves standstill 1h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 3 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, content reaches more than 98%.
Comparative example 1
The reduction transposition of the 6-nitro-1,2,4-sulfonic acid of each 100ml and acid out waste water are placed in beaker, adjust pH to 2.8 with 30% sodium hydroxide, at 25 DEG C, add 0.4g gac, stir decolouring and filter for 1.5 hours, in filtrate, add the FeSO of 0.5mmol again
4, and then add the H that 2ml mass percent concentration is 28% slowly
2o
2, keep temperature-resistant, standing and reacting 1.5h, regulate pH to 9.3 with 30% aqueous sodium hydroxide solution, under stirring, add the Al that massfraction is 20% slowly
2(SO
4)
3solution, adjusts pH to 6.5, leaves standstill 0.5h afterwards.Liquid turbid after described standing sedimentation is filtered.Repeated oxidation, sedimentation, filtration procedure 4 times, filtrate reaches processing requirements, and obtain technical grade sodium sulfate after evaporation concentration, drying, detected result is in table 1.
By standard test method to COD, colourity before and after above embodiment wastewater treatment, and gained sodium sulfate measures, and its detected result is as shown in table 1.
The result of table 1 embodiment 1 ~ 5
Claims (9)
1. a method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate, is characterized in that, comprise the following steps:
(1) in 6-nitro-1,2,4-sulfonic acid waste water, add alkali and regulate its pH value to 2.0 ~ 3.0;
(2) in the waste water mixing up pH value, gac, FeSO is added under stirring
4and H
2o
2carry out oxidizing reaction;
(3) in the waste water after oxidation, add alkali and regulate its pH to 9 ~ 10;
(4) Al is added in the waste water processed to step (3) under stirring
2(SO
4)
3solution, until reaction system pH to 6 ~ 7, sufficient standing sedimentation obtains turbid liquid, filters obtain filtrate to this turbid liquid;
(5) if the filtrate that step (4) obtains reaches processing requirements, then technical grade sodium sulfate is obtained after evaporation concentration, drying; If the filtrate that step (4) obtains does not reach processing requirements, then repeating step (2) ~ (4), until reach processing requirements.
2. Fenton process 6-nitro-1 according to claim 1,2, the method of 4-acid oxysome waste water co-production sodium sulfate, it is characterized in that, described 6-nitro-1,2,4-acid oxysome waste water is 6-nitro-1, in 2,4-acid oxysome production process, one or both composite wastes produced in reduction transposition or acid out step.
3. Fenton process 6-nitro-1 according to claim 1, the method of 2,4-acid oxysome waste water co-production sodium sulfate, is characterized in that, in step (1) and (3), alkali used is one or both in solid sodium carbonate or 25 ~ 35% aqueous sodium hydroxide solutions.
4. the method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to claim 1, is characterized in that, in step (2), and the FeSO added
4for solid, FeSO
4dosage is 1 ~ 10mmol/L;
The H added
2o
2mass percent concentration is 25 ~ 35%, H
2o
2dosage is 5 ~ 20ml/L.
5. the method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to claim 1, it is characterized in that, in step (2), gac dosage is 0.5 ~ 2g/L, at FeSO
4and H
2o
2add before.
6. the method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to claim 1, it is characterized in that, in step (2), temperature of reaction is 25 ~ 50 DEG C, and the reaction times is 1 ~ 2h, and reactive mode is standing.
7. the method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to claim 1, is characterized in that, in step (4), and the Al added
2(SO
4)
3mass percent concentration is 10 ~ 30%.
8. the method for the Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to any one of claim 1 ~ 7, it is characterized in that, the number of times of repeating step (2) ~ (4) is 2 ~ 4 times.
9. the method for Fenton process 6-nitro-1,2,4-sulfonic acid waste water co-production sodium sulfate according to claim 1, is characterized in that, as liquor C OD≤200mg/L, during colourity≤16 times, reach processing requirements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510940078.6A CN105565566B (en) | 2015-12-15 | 2015-12-15 | A kind of method of Fenton processing 6- nitro -1,2,4- acid oxysome waste water co-production sodium sulphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510940078.6A CN105565566B (en) | 2015-12-15 | 2015-12-15 | A kind of method of Fenton processing 6- nitro -1,2,4- acid oxysome waste water co-production sodium sulphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105565566A true CN105565566A (en) | 2016-05-11 |
| CN105565566B CN105565566B (en) | 2018-11-06 |
Family
ID=55876286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510940078.6A Active CN105565566B (en) | 2015-12-15 | 2015-12-15 | A kind of method of Fenton processing 6- nitro -1,2,4- acid oxysome waste water co-production sodium sulphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105565566B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381877A (en) * | 2017-09-05 | 2017-11-24 | 湖北远大富驰医药化工股份有限公司 | A kind of nitromethane treatment method for high-salinity wastewater |
| CN108046403A (en) * | 2017-12-12 | 2018-05-18 | 合肥立方制药股份有限公司 | A kind of processing method of sulfhydryl compound production waste liquid and its application |
| CN111392907A (en) * | 2020-04-03 | 2020-07-10 | 贺利氏贵金属技术(中国)有限公司 | Method for treating waste water |
| CN113292416A (en) * | 2021-06-04 | 2021-08-24 | 枣庄市泰瑞精细化工有限公司 | Production method for preparing sodium acetate by utilizing dihydroxy naphthalene waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516195A (en) * | 2011-12-09 | 2012-06-27 | 江苏远征化工有限公司 | Production method of 6-nitro-1,2,4-sulfonic acid |
| CN102826673A (en) * | 2011-06-15 | 2012-12-19 | 浙江龙盛化工研究有限公司 | Cleaning treatment method of dying industrial acidic wastewater |
| CN104326614A (en) * | 2014-11-12 | 2015-02-04 | 中蓝连海设计研究院 | Comprehensive treatment method of H acid production wastewater |
| CN104609445A (en) * | 2015-03-04 | 2015-05-13 | 黄光秀 | Method for recovering high-purity sodium sulfite from wastewater generated by naphthol preparation |
-
2015
- 2015-12-15 CN CN201510940078.6A patent/CN105565566B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826673A (en) * | 2011-06-15 | 2012-12-19 | 浙江龙盛化工研究有限公司 | Cleaning treatment method of dying industrial acidic wastewater |
| CN102516195A (en) * | 2011-12-09 | 2012-06-27 | 江苏远征化工有限公司 | Production method of 6-nitro-1,2,4-sulfonic acid |
| CN104326614A (en) * | 2014-11-12 | 2015-02-04 | 中蓝连海设计研究院 | Comprehensive treatment method of H acid production wastewater |
| CN104609445A (en) * | 2015-03-04 | 2015-05-13 | 黄光秀 | Method for recovering high-purity sodium sulfite from wastewater generated by naphthol preparation |
Non-Patent Citations (2)
| Title |
|---|
| 李茂: "Fenton-絮凝法处理6-硝还原废水", 《化工管理》 * |
| 陶明杰等: "活性炭协同芬顿试剂处理印染行业生化池出水的研究", 《兵器材料科学与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381877A (en) * | 2017-09-05 | 2017-11-24 | 湖北远大富驰医药化工股份有限公司 | A kind of nitromethane treatment method for high-salinity wastewater |
| CN108046403A (en) * | 2017-12-12 | 2018-05-18 | 合肥立方制药股份有限公司 | A kind of processing method of sulfhydryl compound production waste liquid and its application |
| CN108046403B (en) * | 2017-12-12 | 2021-04-23 | 合肥立方制药股份有限公司 | Treatment method and application of mercapto compound production waste liquid |
| CN111392907A (en) * | 2020-04-03 | 2020-07-10 | 贺利氏贵金属技术(中国)有限公司 | Method for treating waste water |
| CN113292416A (en) * | 2021-06-04 | 2021-08-24 | 枣庄市泰瑞精细化工有限公司 | Production method for preparing sodium acetate by utilizing dihydroxy naphthalene waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105565566B (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105236623B (en) | A kind of processing method of H acid waste water | |
| CN104556521A (en) | Treatment method for condensed wastewater in disperse blue 56 production process | |
| CN103964609A (en) | Membrane treatment method of landfill leachate concentrate | |
| CN105565566A (en) | Method for performing Fenton treatment on 6-nitro-1-diazo-2-naphthol-4-sulfonic acid wastewater and coproducing sodium sulfate | |
| CN110980903A (en) | Preparation method of poly-aluminum ferric silicate flocculant for pretreatment of coking wastewater | |
| CN105130854A (en) | Improved H acid production process | |
| CN104030532B (en) | Weaving face fabric printing-dyeing waste water treatment process | |
| CN105347579A (en) | Improved K acid synthesis technology | |
| US20180257945A1 (en) | Process for potash recovery from biomethanated spent wash with concomitant environmental remediation of effluent | |
| CN104193061A (en) | Treatment method for paraquat pesticide wastewater | |
| CN113101930B (en) | Preparation of copper ferrite-like Fenton catalyst with coral-like morphology and its use in landfill leachate-like Fenton-like catalytic oxidation | |
| CN104926033A (en) | Efficient treatment method for printing and dyeing wastewater | |
| CN105036424A (en) | Recycling wastewater desalination purification method and application thereof | |
| CN117263334B (en) | Method for preparing composite flocculant by using aluminum ash | |
| CN110590024B (en) | Method for treating DSD acid oxidative condensation wastewater | |
| CN116813481B (en) | Recovery treatment method of 2, 5-diaminotoluene sulfate production wastewater | |
| CN117342731A (en) | Treatment method of ferric phosphate wastewater | |
| CN105347578A (en) | Improved 2-naphthol synthesis technology | |
| CN105293757A (en) | New method for preprocessing high-mercury-concentration anthraquinone intermediate wastewater | |
| CN108217815A (en) | A kind of method for removing phosphor in sewage element | |
| CN112759173B (en) | Pretreatment method of trifloxystrobin production wastewater | |
| CN113603264A (en) | Method for treating wastewater in DNS acid reduction section | |
| CN112573723A (en) | Anti-salt-staining S wastewater treatment method and system | |
| CN105366862A (en) | Treatment method of sulfur acid-containing dye wastewater | |
| CN111167453A (en) | Preparation method and application method of catalyst for removing ammonia nitrogen in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |