CN105084600B - A kind of method and its application of efficient process salt-containing organic wastewater - Google Patents
A kind of method and its application of efficient process salt-containing organic wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 61
- 150000003839 salts Chemical class 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 78
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 238000000502 dialysis Methods 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000000706 filtrate Substances 0.000 claims abstract description 30
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 239000012670 alkaline solution Substances 0.000 claims abstract description 23
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012530 fluid Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- YAIKCRUPEVOINQ-UHFFFAOYSA-N 2-aminonaphthalene-1,5-disulfonic acid Chemical group OS(=O)(=O)C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 YAIKCRUPEVOINQ-UHFFFAOYSA-N 0.000 claims description 14
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 claims description 14
- IEXIPYCHASVPFD-UHFFFAOYSA-L disodium;7-hydroxynaphthalene-1,3-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=CC(O)=CC=C21 IEXIPYCHASVPFD-UHFFFAOYSA-L 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 239000003011 anion exchange membrane Substances 0.000 claims description 9
- UBDHSURDYAETAL-UHFFFAOYSA-N 8-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 UBDHSURDYAETAL-UHFFFAOYSA-N 0.000 claims description 8
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 8
- QZZSAWGVHXXMID-UHFFFAOYSA-N 1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 QZZSAWGVHXXMID-UHFFFAOYSA-N 0.000 claims description 6
- ZUQOBHTUMCEQBG-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 ZUQOBHTUMCEQBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004176 ammonification Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 229910021529 ammonia Inorganic materials 0.000 description 14
- 239000005416 organic matter Substances 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 238000002955 isolation Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 5
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000010838 isolation waste Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000909 electrodialysis Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 golden yellow K-RAZ Chemical compound 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- DOBIZWYVJFIYOV-UHFFFAOYSA-N 7-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(O)=CC=C21 DOBIZWYVJFIYOV-UHFFFAOYSA-N 0.000 description 2
- 235000004237 Crocus Nutrition 0.000 description 2
- 241000596148 Crocus Species 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- KSTGSVANFMJGGB-UHFFFAOYSA-N 2-ethylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CC)=CC=C21 KSTGSVANFMJGGB-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical group C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- INOIOAWTVPHTCJ-UHFFFAOYSA-N 6-acetamido-4-hydroxy-3-[[4-(2-sulfooxyethylsulfonyl)phenyl]diazenyl]naphthalene-2-sulfonic acid Chemical compound CC(=O)NC1=CC=C2C=C(C(N=NC3=CC=C(C=C3)S(=O)(=O)CCOS(O)(=O)=O)=C(O)C2=C1)S(O)(=O)=O INOIOAWTVPHTCJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- CHVGJBSUVGBIBE-UHFFFAOYSA-N [Br].OS(O)(=O)=O Chemical compound [Br].OS(O)(=O)=O CHVGJBSUVGBIBE-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- YOCIQNIEQYCORH-UHFFFAOYSA-M chembl2028361 Chemical compound [Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=CC=C1 YOCIQNIEQYCORH-UHFFFAOYSA-M 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- SQYUJKVKVFILNB-UHFFFAOYSA-N methyl 2-amino-4-[(2,5-dichlorophenyl)carbamoyl]benzoate Chemical compound C1=C(N)C(C(=O)OC)=CC=C1C(=O)NC1=CC(Cl)=CC=C1Cl SQYUJKVKVFILNB-UHFFFAOYSA-N 0.000 description 1
- 230000005404 monopole Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of method and its application of efficient process salt-containing organic wastewater, wherein method comprises the following steps：(1) organic wastewater of saliferous is filtered, gained filtrate obtains the organic solution of acid solution or alkaline solution and saliferous through diffusion dialysis；(2) organic solution of saliferous is handled using Bipolar Membrane, obtains containing organic solution, and acid solution and alkaline solution；(3) to carrying out wet oxidation containing organic solution, treatment fluid is obtained；(4) treatment fluid is post-processed, obtains water outlet.The method of efficient process salt-containing organic wastewater provided by the invention, the COD value of waste water can not only be significantly reduced, while the material in waste water is effectively recycled.
Description
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of method of efficient process salt-containing organic wastewater and its
Using.
Background technology
In chemical process, various salt-containing organic wastewaters are inevitably produced, in order to meet the need of environmental protection
Ask, it is necessary to handle these waste water, to reach discharge standard.
Sulpho Tobias Acid, also known as aniline -2,5- disulfonic acid (2- amino is to benzenedisulfonic acid), are a kind of dyestuff intermediates, main
It is used to manufacture direct fast blue RGL, activity Yincui blue KGL, reactive brilliant yellow and reactive orange, fluorescent whitening agent etc..Sulpho Tobias Acid
Containing acid 28% or so, sodium chloride-containing 10% or so, using existing method of wastewater treatment in waste water, it is impossible to which acid therein is carried out
It is effective to recycle.
G salt is white, needle-shaped crystals, and the production of G salt need to pass through sulfonation, saltout, suction strainer three process, and wherein sulfonation is ethylnaphthalene
The secondary sulfonating reaction that phenol is carried out with sulfuric acid, nicotinic acid, after G salt sulfonation, only 64% or so ethyl naphthol is changed into G acid,
The naphtholsulfonic acid for still having more than 30% is trapped in G salt waste water, and wherein main isomer is R acid.By salting-out method make G acid into
Salt out, and R is sour and other accessory substances are remained in G salt waste water.G salt is separated with G salt waste water by filtering, and G salt waste water is in dark
Green, acidity, saliferous, coloured, high concentration, therefore, it is necessary to G salt waste water is acted upon.
K acid, i.e. 2- naphthalenes ammonia -3,6,8- trisulfonic acids, are a kind of important fine-chemical intermediates, are mainly used in such as active
The production of the azo active dyestuffs, acid dyes and organic pigment such as golden yellow K-RAZ, active yellow M-5R, reactive brilliant orange K-7R.
At present the production technology of 2- naphthalenes ammonia -3,6,8- trisulfonic acids be using beta naphthal as raw material through a sulfonation, saltout, ammonia
The processes such as solution, isolation, secondary sulfonation, washing, filtering, drying and be made.K acid waste water has following feature：
(1) acid strong, pH is 0.2~0.6；
(2) colourity is deep, and waste water is in sepia, and colourity is about 5000 times；
(3) pollutant concentration is high, and COD is 2000~3500mg/L, and wherein main component is 2- naphthalene ammonia -3,6, the sulphurs of 8- tri-
Acid, content is 1500~3000mg/L, in addition also containing inorganic salts such as 1.5% or so sodium sulphate；
(4) biodegradation is difficult to, due to 2- naphthalene ammonia -3,6,8- trisulfonic acids have stable naphthalene ring, while in molecule
Containing three sulfonate functional bases for playing passivation, molecular structure is sufficiently stable, biodegradability extreme difference, it is difficult to using biochemical method
Degraded；
(5) toxicity is big, 2- naphthalene ammonia -3,6, and 8- trisulfonic acids belong to condensed-nuclei aromatics, and the amino base containing intoxicating in molecule
Group, has strong bio-toxicity, if not appropriately processed directly discharge, will seriously pollute water environment, and be detrimental to health.
Bromamine acid, also known as 1- amino -4- bromo anthraquinone -2- sulfonic acid, are mainly used in dyestuff intermediate.The production method of bromamine acid
1- amino anthraquinones is used as raw material more, oleum sulfonation is used in concentrated sulfuric acid medium, and then smoke is used in concentrated sulfuric acid medium
Sulfuric acid bromine bromination, through diluting, neutralizing, the step such as refining and be made, a large amount of waste water are produced in production process.
The mode of existing processing industrial wastewater is varied, is reduced by various physical chemistry and biological means in waste water
Pollutant load, for example, existing H acid isolation waste water processing method be：First, H acid isolation waste water is extracted；So
Afterwards, carry out concentrating salt steaming, obtained sodium sulphate does fixed-end forces or reuse.Due to the excess production capacity of sodium sulphate, and concentrate
The cost height of salt steaming, the sodium sulfate salt inferior quality obtained, application are narrow.
Diffusion dialysis as a kind of membrane separation technique using concentration difference as motive force, using translucent or selective penetrated property from
Proton exchange makes the solute in solution be migrated from high concentration side by film to low concentration side.Due to its have it is simple to operate,
Energy consumption is low, non-secondary pollution, the advantages that being easily coupled with other techniques, be widely used in the fields of various generation spent acid alkali.
The core of diffusion dialysis is：1st, the concentration difference of amberplex both sides solution；2nd, the selection of amberplex is saturating
The property crossed.Divided according to the species of amberplex, anion-exchange membrane diffusion dialysis can be divided into and cation exchange membrane diffusion oozes
Analysis.Anion-exchange membrane diffusion dialysis is mainly used to the acid in recovery acid salt mixture, and cation-exchange membrane diffusion dialysis is main
For reclaiming the alkali in alkali salt mixture.
Bipolar membrane electrodialysis is the electrodialysis that Bipolar Membrane differently combines formation with monopole film, by common electrodialysis
Salt dissociation be combined together with the dissociation of the hydrone of Bipolar Membrane, make corresponding salt ion and the production of Bipolar Membrane water decomposition in solution
Raw H+And OH-With reference to being converted into corresponding bronsted lowry acids and bases bronsted lowry.Inorganic salts and organic salt can be converted on the membrane stack of same Bipolar Membrane
Corresponding bronsted lowry acids and bases bronsted lowry.
Nowadays it is double due to commonly using neutralization reaction, generating substantial amounts of brine waste in many chemical process
Pole EDBM can change into the salt in brine waste corresponding bronsted lowry acids and bases bronsted lowry, while can be used for the bronsted lowry acids and bases bronsted lowry that recovery obtains
The neutralization reaction of Chemical Manufacture.
The content of the invention
The invention provides a kind of method of efficient process salt-containing organic wastewater, the COD of waste water can not only be significantly reduced
Value, moreover it is possible to effectively recycled to the material in waste water.Meanwhile using method of the present invention, can be to partly having
The production technology of machine product is improved, and realizes clean manufacturing.
A kind of method of efficient process salt-containing organic wastewater, comprises the following steps：
(1) organic wastewater of saliferous is filtered, gained filtrate obtains acid solution or alkalescence is molten through diffusion dialysis
The organic solution of liquid and saliferous；
(2) organic solution of saliferous is handled using Bipolar Membrane, obtains containing organic solution, and acid solution
And alkaline solution；
(3) to carrying out wet oxidation containing organic solution, treatment fluid is obtained；
(4) treatment fluid is post-processed, obtains water outlet.
Method provided by the invention is applied to the organic wastewater of all kinds of saliferous, including the acid waste water of saliferous and saliferous
Alkaline waste water.For example, 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 use industrial continuous production, i.e. the organic wastewater of saliferous is continuous successively
The processing procedure of step (1)~step (4) is undergone, obtains standard compliant relief liquor.
Method provided by the invention filters to industrial wastewater (i.e. the organic wastewater of saliferous) first, is suspended with removing
The solid matter such as thing and iron, calcium, magnesium, then passed through using the selection of semipermeable membrane or perm-selective ion-ex-change membrane to filtrate
Effect, filtrate is separated into the organic solution of acid solution and saliferous, and acid solution direct reuse contains into corresponding workshop section
The organic solution of salt is then further separated using Bipolar Membrane, obtains acid solution and alkaline solution, and containing organic
The solution of thing, the solution containing organic matter utilize wet oxidation, are small molecule by organic matter degradation, are finally removed using decolorising agent aobvious
Color substance, complete the processing of waste water.
Preferably, in step (1) diffusion dialysis reaction condition：Anion-exchange membrane is used to the acid waste water of saliferous
Dialysis is diffused, dialysis is diffused using cation-exchange membrane to the alkaline waste water of saliferous.
Preferably, in step (2) Bipolar Membrane reaction condition：Individual membrane voltage<2.5V, 100~600A/ of current density
m2, temperature be 1~40 DEG C, electrode solution use mass fraction for 1%~5% metabisulfite solution.
The purpose of wet oxidation reduces COD value, due to wet oxidation in being small molecule by the organic matter degradation in solution
Condition it is more harsh, use, equipment caused damage for a long time inevitably, it is excellent in order to take into account the effect of wet oxidation
Selection of land, the reaction condition of wet oxidation in step (3)：PH is 2~12, and pressure is 2~8MPa, and temperature is 180~300 DEG C, instead
It is 2~6h between seasonable.
Further preferably, in step (3) wet oxidation reaction condition：PH is 4~9, and pressure is 2~6MPa, and temperature is
230~270 DEG C, the reaction time is 3~5h.
Further preferably, in step (3) wet oxidation reaction condition：PH is 7~8, and pressure be 2~4MPa, temperature for 250~
270 DEG C, the reaction time is 3~5h.
COD value significantly reduces after wet oxidation, obtains needing further to be post-processed in treatment fluid, water outlet is obtained, after described
Processing can be to add decolorising agent to remove substance that show color, in order to reach preferable decolorizing effect, it is preferable that used in step (4)
Adsorbent post-processes to treatment fluid.
Treatment fluid is post-processed according to adsorbent, the addition of adsorbent for treatment fluid quality 0.05~
0.5%, 20~60min of stirring reaction.
Present invention also offers a kind of production technology of improved Sulpho Tobias Acid, bisnaphthol successively by sulfonation, neutralization,
Distillation, ammonification, acidifying, tobias acid sulfonation, hydrolyze, saltout, washing and obtain Sulpho Tobias Acid, waste water caused by Sulpho Tobias Acid according to
Secondary filtered and diffusion dialysis, obtained sulfuric acid reuse to acid out workshop section.
Containing the sulfuric acid that mass fraction is 28% or so in Sulpho Tobias Acid waste water, and mass fraction is 10% or so
Sodium chloride, Sulpho Tobias Acid waste water is handled using method provided by the invention, can effective recycling sulfuric acid, improve
The utilization rate of raw material.
Diffusion dialysis and Bipolar Membrane in the present invention can separate the acidic materials in handled solution, weight
New reuse realizes the effective recycling of component in waste water, has saved the resources of production again into required workshop section.
The present invention compared with prior art, has the advantages that：
(1) processing method provided by the invention can significantly reduce the COD value in waste water, COD clearance 96% with
On；
(2) processing method provided by the invention uses diffusion dialysis and bipolar film process to waste water, and obtained bronsted lowry acids and bases bronsted lowry returns
With into corresponding production workshop section, the utilization rate of raw material is improved.
(3) processing method provided by the invention is suitable to continuous production, is easy to industrially popularization and application.
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 suspension and iron, calcium, magnesium.
(2) diffusion dialysis：Filtrate is handled using anion-exchange membrane diffusion dialysis, dialysis obtains sulfuric acid and saliferous
Organic solution, the rate of recovery 90% of sulfuric acid.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
10% sulfuric acid, the mass fraction of sodium hydroxide is 4% in alkaline solution, and the mass fraction of ammonia is 4%.The reaction bar of Bipolar Membrane
Part：Individual membrane voltage is 2.5V, current density 600A/m2, temperature be 30 DEG C, electrode solution use mass fraction for 5% sulphur
Acid sodium solution.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 7, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 2h.
Measure out kettle waste water and show orange-yellow, pH=4.5, COD=2083mg/L, NH3- N=164.2mg/L.
(5) adsorb：The kettle waste water that goes out of step (4) is adjusted to neutral pH=7, adds mass fraction as 0.2% (with regulation
On the basis of the quality of waste water after pH) activated carbon stirring and adsorbing 0.5h after filter, obtained slightly yellow filtrate, then add quality
Fraction is 0.3% activated carbon (on the basis of the quality of the waste water after adjusting pH) stirring and adsorbing 30min, and suction filtration obtains transparent place
Manage liquid, COD=150mg/L, salt content 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 suspension and iron, calcium, magnesium.
(2) diffusion dialysis：Filtrate is handled using anion-exchange membrane diffusion dialysis, dialysis obtains sulfuric acid and saliferous
Organic solution.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
9% sulfuric acid, the mass fraction of sodium hydroxide is 3.9% in alkaline solution, and the mass fraction of ammonia is 3.5%.Bipolar Membrane it is anti-
Answer condition：Individual membrane voltage is 2V, current density 400A/m2, temperature is 30 DEG C, and electrode solution uses 5% metabisulfite solution.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 8, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 1.5h.
Measure out kettle waste water and show orange-yellow, pH=4.5, COD=2483mg/L, NH3- N=165.0mg/L.
(5) adsorb：Step (4) go out in kettle waste water add mass fraction be 0.3% activated carbon (to go out kettle waste water
On the basis of quality) stirring and adsorbing 30min, filter and obtain yellowish treatment fluid, 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 suspension and iron, calcium, magnesium.
(2) diffusion dialysis：Filtrate is handled using anion-exchange membrane diffusion dialysis, is acted on through diffusion dialysis, obtains sulphur
The organic solution of acid and saliferous.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
11% sulfuric acid, the mass fraction of sodium hydroxide is 4.5% in alkaline solution, and the mass fraction of ammonia is 4.5%.Bipolar Membrane it is anti-
Answer condition：Individual membrane voltage is 2.5V, current density 600A/m2, temperature is 30 DEG C, and electrode solution is molten using 5% sodium sulphate
Liquid.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted 7, then adds high pressure
In kettle, 30atm air is passed through, is cooled after being reacted one hour at 250 DEG C；
Pressure release after cooling, the air for being further continued for being passed through 30atm continue to cool after reacting one hour at 250 DEG C；
After cooling pressure release, then 30atm air is passed through, is reacted 1.5 hours at 250 DEG C.Water outlet yellow, COD=
6500mg/L, COD clearance 95%.
(5) decolourize：It is that 0.3% activated carbon (goes out water quality with step (4) that mass fraction is added into the water outlet of step (4)
On the basis of amount), filter after stirring and adsorbing 30min, then filtered after adding the charcoal absorption that mass fraction is 0.1%, filtrate is shallow
Yellow, survey COD=6000mg/L or so.
Comparative example 1
It is that step (5) uses ClO with the difference of embodiment 32Decolourize, concrete operations are as follows：
0.2% ClO is added in water outlet to step (4)2(ClO2Dosage on the basis of the effluent characteristics of step (4)),
30min is reacted under normal temperature, the activated carbon (on the basis of effluent characteristics of step (4)) that mass fraction is 0.1% is added and adsorbs
Filtered after 30min, color is crocus, and decolorizing effect is undesirable.
Comparative example 2
It is that step (5) is decolourized using Fe/C with the difference of embodiment 3, concrete operations are as follows：
The water outlet pH=4 of pacing rapid (4), adds that mass fraction is 0.2% activated carbon and mass fraction is 2% iron powder (with step
Suddenly on the basis of the effluent characteristics of (4)) filter after reaction 4h, then pH=8 is adjusted to, is filtered after the 30min that flocculates, filtrate is crocus,
Decolorizing effect is undesirable.
Embodiment 4
(1) refined naphthalene is sulfonated successively, nitrifies, neutralize, reducing, the sour isolations of T, alkali fusion, H acid isolate and H acid is prepared.
(2) filter：H acid isolation waste water is filtered, to remove the material such as suspension and iron, calcium, magnesium.
(3) diffusion dialysis：Filtrate is handled using anion-exchange membrane diffusion dialysis, dialysis obtains sulfuric acid and saliferous
Organic solution.
(4) bipolar film process：The saliferous organic solution obtained using Bipolar Membrane processing step (3), obtains alkaline solution
With the sulfuric acid that mass fraction is 9.8%, the mass fraction of sodium hydroxide is 3.7% in alkaline solution, and the mass fraction of ammonia is
3.7%.The reaction condition of Bipolar Membrane：Individual membrane voltage is 2V, current density 450A/m2, temperature is 30 DEG C, and electrode solution uses
5% metabisulfite solution.
By sulfuric acid reuse obtained by the step to H acid isolations workshop section, gained alkaline solution is rotated, obtains sodium hydroxide
Reuse is to alkaline melt workshop section.
(5) wet oxidation：The pH of the solution containing organic matter obtained after step (4) bipolar film process is adjusted to 7, then
Squeeze into wet oxidation kettle, be warming up to 250 DEG C, pressure 6MPa, cool after being passed through air oxidation 1.5h.
Measure out kettle waste water and show orange-yellow, pH=4.5, COD=2107mg/L.
(6) adsorb：Step (5) go out in kettle waste water add mass fraction be 0.2% activated carbon (with step (4)
Go out on the basis of kettle wastewater quality) stirring and adsorbing 30min, filter and obtain flaxen treatment fluid, then adjust pH to 6.0, color
Be changed into yellow, then add activated carbon that mass fraction is 0.3% (by step (4) go out kettle wastewater quality on the basis of) stirring and adsorbing
30min, suction filtration obtain yellowish treatment fluid, its COD=1487mg/L.
(7) filter：T acid isolation waste water is filtered, to remove the material such as suspension and iron, calcium, magnesium.
(8) diffusion dialysis：Filtrate obtained by step (7) is handled using anion-exchange membrane diffusion dialysis, dialysis obtains
To sulfuric acid and the organic solution of saliferous.
(9) bipolar film process：Using the saliferous organic solution of Bipolar Membrane processing step (8), alkaline solution and matter are obtained
The sulfuric acid that fraction is 9.8% is measured, by sulfuric acid reuse to T acid isolations workshop section.
The reaction condition of Bipolar Membrane：Individual membrane voltage is 2V, current density 450A/m2, temperature is 30 DEG C, and electrode solution is adopted
With 5% metabisulfite solution.
(10) wet oxidation：The pH of the solution containing organic matter obtained after step (9) bipolar film process is adjusted to 8, added
Enter the CuSO that mass fraction is 0.5%4·5H2O as catalyst (by T acid isolation wastewater quality on the basis of), 260 DEG C of temperature,
3h is reacted under the conditions of pressure 7MPa, reaction filters after terminating and obtains the filtrate (i.e. filtrate I) of chartreuse, its pH=2.1 or so,
COD clearances are 85%.
(11) FeSO that mass fraction is 0.5% is added into filtrate I4·7H2O is (using T acid isolation wastewater qualities as base
It is accurate), treat FeSO4·7H2After O is completely dissolved, adds the liquid caustic soda that mass fraction is 5.5% and adjust pH=8.5, flocculate 30min, takes out
Filter obtains the filtrate II of blueness.
(12) Na that mass fraction is 0.6% is added in filtrate II2S·9H2O is (using T acid isolation wastewater qualities as base
It is accurate), react 30min, remove complex copper, suction filtration obtains filtrate III as black (CuS particles are smaller, partly into filtrate).
(13) concentrated sulfuric acid that mass fraction is 0.6% is added in filtrate III and adjusts back pH=6.0, adding mass fraction is
0.2% activated carbon (on the basis of T acid isolation wastewater qualities) absorption 30min, obtains subdiaphanous filtrate, its COD clearance is
96%.
Embodiment 5
(1) tobias acid is sulfonated successively, Sulpho Tobias Acid is prepared in acid out, press filtration；
(2) filter：Sulpho Tobias Acid waste water is filtered, to remove the material such as suspension and iron, calcium, magnesium.
(3) diffusion dialysis：Filtrate obtained by step (2) is handled using anion exchange EDBM, dialysis obtains
The organic solution of sulfuric acid and saliferous.
(4) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
10% sulfuric acid, the mass fraction of sodium hydroxide is 4% in alkaline solution, and the mass fraction of ammonia is 4%.The reaction bar of Bipolar Membrane
Part：Individual membrane voltage is 2V, current density 500A/m2, temperature is 30 DEG C, and electrode solution uses 5% metabisulfite solution.
(5) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 7, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 2h.The COD clearances for measuring out kettle waste water are
96%.
(6) adsorb：The kettle waste water that goes out of step (5) is adjusted to neutral pH=7, adds mass fraction as 0.5% (with regulation
On the basis of the quality of waste water after pH) activated carbon stirring and adsorbing 0.5h after filter, obtained filtrate is almost colourless transparent, COD
=150mg/L, salt content 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 matters such as suspension and iron, calcium, magnesium in waste water.
(2) filtrate is handled using anion exchange EDBM, dialysis obtains sulfuric acid and the organic matter of saliferous is molten
Liquid, the rate of recovery 92% of sulfuric acid.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
10% sulfuric acid, the mass fraction of sodium hydroxide is 4% in alkaline solution, and the mass fraction of ammonia is 3.8%.The reaction of Bipolar Membrane
Condition：Individual membrane voltage is 2V, current density 600A/m2, temperature is 30 DEG C, and electrode solution uses 5% metabisulfite solution.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 7, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 2h.
Measure out kettle wastewater pH=4.5, COD=3156mg/L, NH3- N=215mg/L.
(5) adsorb：The kettle waste water that goes out of step (4) is adjusted to neutral pH=7, adds mass fraction as 0.5% (with regulation
On the basis of the quality of waste water after pH) activated carbon stirring and adsorbing 0.5h after filter, obtained filtrate is almost colourless transparent, COD
=596mg/L, salt content 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 suspension and iron, calcium, magnesium.
(2) filtrate is handled using pellicle, is acted on through diffusion dialysis, obtain the organic solution of sulfuric acid and saliferous, sulphur
The rate of recovery 90% of acid.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
11% sulfuric acid, the mass fraction of sodium hydroxide is 4.2% in alkaline solution, and the mass fraction of ammonia is 3.9%.Bipolar Membrane it is anti-
Answer condition：Individual membrane voltage is 2V, current density 500A/m2, temperature is 30 DEG C, and electrode solution uses 5% metabisulfite solution.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 7, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 2h.
Measure out kettle wastewater pH=4.5, COD=3286mg/L, NH3- N=164.2mg/L.
(5) adsorb：The kettle waste water that goes out of step (4) is adjusted to neutral pH=7, adds mass fraction as 0.5% (with regulation
On the basis of the quality of waste water after pH) activated carbon stirring and adsorbing 0.5h after filter, obtained filtrate is almost colourless transparent, COD
=980mg/L, salt content 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 suspension and iron, calcium, magnesium.
(2) filtrate is handled using pellicle, is acted on through diffusion dialysis, obtain the organic solution of sulfuric acid and saliferous, sulphur
The rate of recovery 91% of acid.
(3) bipolar film process：Using the organic solution of bipolar film process saliferous, obtain alkaline solution and mass fraction is
9.8% sulfuric acid, the mass fraction of sodium hydroxide is 3.9% in alkaline solution, and the mass fraction of ammonia is 3.7%.Bipolar Membrane
Reaction condition：Individual membrane voltage is 2V, current density 450A/m2, temperature is 30 DEG C, and electrode solution is molten using 5% sodium sulphate
Liquid.
(4) wet oxidation：The pH of the solution containing organic matter obtained after bipolar film process is adjusted to 7, then squeezes into wet type
In stills for air blowing, 250 DEG C, pressure 6MPa are warming up to, is cooled after being passed through air oxidation 2h.
Measure out kettle wastewater pH=4.5, COD=1956mg/L, NH3- N=158mg/L.
(5) adsorb：The kettle waste water that goes out of step (4) is adjusted to neutral pH=7, adds mass fraction as 0.4% (with regulation
On the basis of the quality of waste water after pH) activated carbon stirring and adsorbing 0.5h after filter, obtained filtrate is almost colourless transparent, COD
=358mg/L, salt content 3.7%.
Claims (4)
- A kind of 1. method of efficient process salt-containing organic wastewater, it is characterised in that comprise the following steps：(1) organic wastewater of saliferous is filtered, gained filtrate through diffusion dialysis, obtain acid solution or alkaline solution with And the organic solution of saliferous, described organic wastewater is Sulpho Tobias Acid sour water, K acid waste water, G salt waste water, bromamine acid give up Water, T acid waste water or H acid waste water；(2) organic solution of saliferous is handled using Bipolar Membrane, obtains containing organic solution, and acid solution and alkali Property solution；(3) it is 2~12 in pH, pressure is 2~8MPa, under conditions of temperature is 180~300 DEG C, to being carried out containing organic solution Wet oxidation, obtain treatment fluid；The wet oxidation reaction time is 2~6h；(4) treatment fluid is post-processed using adsorbent, obtains water outlet；The addition of adsorbent for treatment fluid quality 0.05~ 0.5%, 20~60min of stirring reaction.
- 2. the method for efficient process salt-containing organic wastewater as claimed in claim 1, it is characterised in that diffusion is oozed in step (1) The reaction condition of analysis：Dialysis is diffused using anion-exchange membrane to the acid waste water of saliferous, the alkaline waste water of saliferous is adopted Dialysis is diffused with cation-exchange membrane.
- 3. the method for efficient process salt-containing organic wastewater as claimed in claim 1, it is characterised in that Bipolar Membrane in step (2) Reaction condition：Individual membrane voltage<2.5V, 100~600A/m of current density2, temperature is 1~40 DEG C, and electrode solution uses quality Fraction is 1%~5% metabisulfite solution.
- 4. a kind of production technology of improved Sulpho Tobias Acid, bisnaphthol successively by sulfonation, neutralization, distillation, ammonification, acidifying, Tobias acid sulfonation, hydrolyze, saltout, washing and obtain Sulpho Tobias Acid, it is characterised in that waste water caused by Sulpho Tobias Acid is using such as The method of efficient process salt-containing organic wastewater described in any one of claims 1 to 3 is handled, obtained sulfuric acid reuse to acid Analyse workshop section.
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| CN105566176B (en) * | 2015-11-26 | 2018-06-22 | 浙江奇彩环境科技股份有限公司 | A kind of production technology of the sour oxysome of improved 6- nitros -1,2,4 |
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| 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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