CN103011492A - Method for treating waste water from semiconductor process - Google Patents
Method for treating waste water from semiconductor process Download PDFInfo
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- CN103011492A CN103011492A CN2012100672495A CN201210067249A CN103011492A CN 103011492 A CN103011492 A CN 103011492A CN 2012100672495 A CN2012100672495 A CN 2012100672495A CN 201210067249 A CN201210067249 A CN 201210067249A CN 103011492 A CN103011492 A CN 103011492A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims abstract description 73
- 230000008569 process Effects 0.000 title claims abstract description 42
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000011282 treatment Methods 0.000 claims abstract description 20
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 126
- 238000010521 absorption reaction Methods 0.000 claims description 35
- 238000001223 reverse osmosis Methods 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 29
- 239000010802 sludge Substances 0.000 claims description 22
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 17
- 230000014759 maintenance of location Effects 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
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- 238000000926 separation method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 244000005700 microbiome Species 0.000 abstract description 6
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- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000000813 microbial effect Effects 0.000 abstract description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 2
- 239000005416 organic matter Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 9
- 230000033228 biological regulation Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000005374 membrane filtration Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000026676 system process Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- SEJUQQOPVAUETF-QHLBDZCJSA-N (2r,6r,11s)-3-(cyclopropylmethyl)-6-ethyl-8-hydroxy-11-methyl-3,4,5,6-tetrahydro-2,6-methano-3-benzazocin-1(2h)-one Chemical compound C([C@@]1([C@@H]([C@@H]2C(=O)C=3C1=CC(O)=CC=3)C)CC)CN2CC1CC1 SEJUQQOPVAUETF-QHLBDZCJSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating comprehensive wastewater integrated by a plurality of strands of semiconductor process wastewater, wherein the comprehensive wastewater does not contain NH4F/HF Buffered Oxide Etch solution wastewater (NH for short)4F/F-waste water) and essentially contains oxidants, organic matter, inorganic matter, and ammonia nitrogen impurities. Firstly, carrying out deoxidant removal treatment on the comprehensive wastewater; then, the impurities contained in the wastewater are partially decomposed by anaerobic microbial decomposition; then the organic matter and ammonia nitrogen remained in the wastewater are further decomposed by the aerobic microorganism decomposition method, and the recoverable or discharged wastewater is obtained. The process of the invention further comprises reacting NH4OH leaching wastewater, TMAH yellow light process wastewater, or NH4F/F-A step of treating the waste water individually, and a method of treating the waste water obtained by the individual treatments by integrating the waste water into the comprehensive waste water.
Description
Technical field
The present invention system is about a kind for the treatment of process of semiconductor technology waste water, provides a kind of and contains oxygenant, organism, inorganics, and the impurity such as ammonia nitrogen and compiled the treatment process of the comprehensive wastewater that forms by several strands of semiconductor technology waste water, and can comprise NH
4The OH wastewater eluting is processed, TMAH (Tetramethylammonium hydroxide) gold-tinted processing wastewater is processed or NH
4F/F
-The individual treated such as wastewater treatment.
Background technology
The recycling of water becomes necessary scheme in the epoch of at present climatic anomaly transition to high water consumption industry; Factory relies on and must significantly reduce external water source, to reduce the upper uncertain factor of producing.Water rate of recovery height has solved the problem of producing upper uncertain factor, but also produces another subject under discussion: the environment protection emission problem that exceeds standard.The amount of chemicals used that factory uses is fixed, in case the rate of recovery of water is high, causes the discharge reduction that discharges; Identical pharmaceutical chemicals consumption has caused the problem of discharge of wastewater excessive concentration, thereby exceeds standard.For the subject under discussion of environment, the unit of national environmental protection is also for some materials of finding environment is had a bad impact because of current research result strict supervision in addition, such as ammonia nitrogen, total nitrogen (TN), total phosphorus (TP).Though also have the existing control of some water quality standard of releasing, still may need stricter control in future, such as biochemical oxygen demand (BOD) (BOD), chemical oxygen demand (COD) (COD), and suspended solids (SS).Therefore the recycling of water resources has also affected the subject under discussion of environmental protection; This recovery is the important topic of national development with the subject under discussion of taking into account environmental protection.
The kind of the contained pollutent of semi-conductor industrial waste water complicated (containing organic and inorganic, oxide compound, ammonia nitrogen and fluorochemical etc.), present semiconductor factory is will classify accurately through the used water of technique first for the strategy of water treatment, and the most extreme practice is that its minute made 22 class waste water at present.The direct collection that impure concentration is lower is reclaimed and is made the water source; High the reclaiming again after RO, ion-exchange or coagulating sedimentation are processed of any of some impurity is used as the water source; Remaining water is just directly done the waste water discharging.The discharge of wastewater of existing semiconductor factory is that the inner different process waste water of semiconductor factory progressively compiles and becomes one to three strand of large amount of complex wastewater, accumulates one again and discharges factory.These several strands a large amount of waste water or upstream be the numerous confusion of waste water title of system in a small amount, but mostly named according to its water quality content as follows, such as comprehensive wastewater, NH
4F/F
-Waste water, F
-Waste water, high density ammonia wastewater eluting, central wastewater eluting, TMAH gold-tinted waste water, ozone washing water, pure water system backwash water etc.Because each electronics Product Process medicines different, that used are different, add that planning leading portion waste water reclamation situation is different with the processing wastewater Classification of water Qualities when founding the factory, therefore the variation of each composition a large amount of and in a small amount system waste water of each factory, water quality is quite large.Table 1 is the water quality scope that illustrates comprehensive wastewater.This comprehensive wastewater is cognitive one of rear discharge factory of compiling on the general custom.Recycle-water can be used as the water source of ultrapure water or the water source of secondary water by its water quality.So to the classification arrangement through the used waste water carefulness of technique, the rate of recovery of most of factory in fact still is difficult to reach 85% the rate of recovery of regulation legally, reason is to there is no much more so water yields according to such classification can be collected and reclaim, also so can't reach 85% the rate of recovery.The simultaneously also not reduction of essence of water consumption of full factory, reason are the present practices for being the usefulness of secondary water with recycle-water is multiplex.This is because there is no effective treatment technology at present, affect the water quality of ultrapure water for worrying that recycle-water reclaims as the ultrapure water water source, and then affect the manufacturing good rate of wafer, therefore only the recycle-water of minority per-cent for the water source of ultrapure water system; And the water consumption of ultrapure water is to reach 70～80% of the full station-service water yield, if so recycle-water do not move and be used as this, the water consumption of whole factory is difficult to reduce.Simultaneously in order to process and the event of environment protection emission, be necessary to understand pharmaceutical chemicals that the technique that contains in the waste water uses such as organism (Virahol (isopropyl alcohol, IPA), acetone (acetone), acetic acid (acetic acid), EKC, NMP, TMAH, tensio-active agent), soda acid (HCl, H
2SO
4, HNO
3, NH
4OH, NH
3Gas, H
3PO
4, HF, NH
4F), strong oxidizer (H
2O
2, ozone water), and silicon wafer and the reacted SiO of pharmaceutical chemicals
2The water vent of the in addition backwash water of ultrapure water system (containing Ca and Mg hardness ions and backwash medicament such as NaOH, HCl), and tail gas treatment device (Scrubber) is discharged into waste water and discharges factory.Wherein Virahol produces the conditional acetone of environmental regulation (concentration must less than 3ppm (mg/L)) with strong oxidizer reaction again, produces new problem.Except the discharging of present environmental regulation regulation Virahol and acetone is less than 3ppm, nitrate nitrogen (NO
3 --N) less than 50ppm; New environmental regulation trend is that the concentration of estimating discharge of wastewater is wanted ammonia nitrogen＜10～30ppm, and total nitrogen is less than 50ppm, and total phosphorus is less than 10ppm, and COD is less than 60ppm.Although still in the acceptance of inquiring after industry, these materials are harmful to environment the new legislation draft, and this is the trend in the world, and are finally irresistible.Therefore really carrying out the rate of recovery, really fall the whole station-service water yield in the end, take into account simultaneously environment protection emission, take into account service water autonomous, make safety dumping and make to reclaim the trend that is inevitable from waste water.
Table 1 illustrates the water quality scope of comprehensive wastewater
| Water quality | Comprehensive wastewater |
| Temperature (℃) | 21.3～22.7 |
| pH | 1.5～2.29 |
| Turbidity (Turbidity) (NTU) | 0.0857～0.405 |
| SS(mg/L) | ND |
| H 2O 2(mg/L) | 50～3000 |
| COD(mg/L) | 300～1200 |
| TOC(mg/L) | 250～500 |
| BOD(mg/L) | 220～500 |
| Na 2+(mg/L) | 2～3 |
| K +(mg/L) | ND |
| Ca 2+(mg/L) | 3～29 |
| Mg 2+(mg/L) | 0.8～7 |
| TKN(mg/L) | 100～500 |
| TN(mg/L) | 100～600 |
| NH 4 +-N(mg/L) | 65～408 |
| NO 3 --N(mg/L) | 0.2～11 |
| PO 4 3-(mg/L) | 4～95 |
| SO 4 2-(mg/L) | 2440～6750 |
| F -(mg/L) | 3～7 |
| Cl - | 47～114 |
| SiO 2(mg/L) | 0.8～4 |
| Fe(mg/L) | 0.5 |
| Specific conductivity (Conductivity) (μ s/cm) | 13400～110000000 |
Taiwan patent of invention 313187 discloses a kind of Waste Water Treatment that contains organic pollutant, comprises an anaerobic reaction groove, an aerobic reaction groove, and a membrane sepn groove; Wherein aforementioned aerobic reaction groove is to be arranged at after the anaerobic reaction groove, and aforementioned films separator tank system is arranged at after the aforementioned aerobic reaction groove, and this system of system utilizes the organic pollutant in the biological treatment removal waste water, and with membrane sepn solid-liquid two-phase.Patented invention before this focus on solving film surface scale and incrustation problem, mention especially that wherein this aerobic reaction groove can improve the wherein pH value of processed water, make metal ion wherein form the carbonic acid crystalline particle, and the biological pectisation of mat embeds this carbonic acid metallic crystal particle and has in the flco of oxygen animalcule, forms the tendency of fouling at the film of membrane sepn groove to reduce the metallic crystal thing.The embodiment of patent before this only tests as artificial substratum to contain glucose and sodium-acetate, and not mentioned treatment process to the semiconductor technology waste water that contains oxygenant, organic and ammonia nitrogen pollutant.
Summary of the invention
A main purpose of the present invention namely is to provide a kind of complicated waste water for semiconductor technology to process to reach the technology that emission standard and recovery re-use.
The treatment process of a kind of semiconductor technology waste water provided by the present invention comprises the following step:
A) will be compiled by several strands of semiconductor technology waste water and form the comprehensive wastewater that contains oxygenant, organic impurities and inorganics impurity and carry out the deoxidation agent and process, this comprehensive wastewater does not contain in fact NH
4F/F
-Waste water;
B) process the waste water that is lowered from step oxygenate content a) with anaerobic (anoxic) microorganism is olation, so that wherein contained impurity partly decomposes; And
C) process from step b with aerobic (aerobic) microorganism is olation) the waste water that is lowered of foreign matter content so that the impurity that residues in is wherein further decomposed, reclaim or discharge water and obtain one first.
The inventive method further comprises NH
4OH wastewater eluting, TMAH gold-tinted processing wastewater or NH
4F/F
-Waste water carries out the step of individual treated.
This NH
4The OH wastewater eluting is carried out a degassed/absorption and processes, and it comprises adjusts NH
4The pH value of OH waste water is extremely more than or equal to 10; Continue to aerating wastewater for some time, so from waste water, blow out NH
3, and obtain the first part processing water that ammonia-nitrogen content reduces; And will include from the gas importing one that liquid level is emerged the air-breathing district of absorption agent, so with NH contained in the gas
3Be absorbed on this absorption agent.
As this NH
4The contamination level of OH wastewater eluting (the concentration x water yield) is little of step b with respect to this comprehensive wastewater person) can bear without the oxygen animalcule is olation time, its can be merged by the waste water that the oxygenate content that a) flows out with above-mentioned steps is lowered together carry out step b) and c).
This TMAH gold-tinted processing wastewater is carried out a biological anaerobic treatment, comprise this TMAH gold-tinted processing wastewater is imported a biological anaerobism groove, and be stranded in wherein 5～48 hours and TMAH is decomposed by anaerobion wherein, process water and discharge one second part, wherein the redox potential of the waste water in this groove is-200 to-500mV.
When the contamination level of this TMAH gold-tinted processing wastewater little of step b with respect to this comprehensive wastewater person) can bear without the oxygen animalcule is olation time, its can be merged by the waste water that the oxygenate content that a) flows out with above-mentioned steps is lowered together carry out step b) and c).
This first part is processed water and the second part and is processed water and together carried out step b by the waste water merging that the oxygenate content that a) flows out with above-mentioned steps is lowered) and c).
This NH
4F/F
-Waste water is carried out a degassed/absorption and processes, and comprises and adjusts NH
4F/F
-The pH value of waste water is extremely more than or equal to 10; Continue to aerating wastewater for some time, so from waste water, blow out NH
3To include from the gas importing one that liquid level is emerged the air-breathing district of absorption agent, so with NH contained in the gas
3Be absorbed on this absorption agent; The waste water of sloughing the part ammonia nitrogen then is carried out F
-Process, comprise reverse osmosis or add CaCl
2, reclaim or discharge water and obtain one second.If F
-Concentration＞400ppm, then this removes F
-Processing comprises and adds CaCl
2, produce CaF
2Precipitation; Solid-liquid separation, directly CaF is removed in discharging
2The waste water of precipitation, at this moment its F
-Concentration＜15ppm.If F
-Concentration is not more than 400ppm, and then this removes F
-Processing comprises reverse-osmosis treated, and the reverse osmosis water that obtains is regarded as one the 3rd and reclaims or discharge water, is recovered as preferably to be imported into a refining system; Contain F and this reverse osmosis produces
-The dense row of ion holds the waste water can be by adding CaCl
2Mode is removed F wherein
-Ion is discharged again.
If there is other to contain F in the technique
-Waste water, its can with NH
4F/F
-Degassed/absorption that waste water is carried out is processed resulting this and is sloughed NH
3Waste water together carry out this and remove F
-Process.
NH
3The suitable example of absorption agent has phosphoric acid, sulfuric acid or water.
By above-mentioned steps c) flow out first reclaim or discharge water can be used for diluting this NH by the shunting some
4F/F
-Waste water makes it be fit to carry out this degassed/absorption and processes.
By above-mentioned steps c) if first recovery of flowing out or discharge water reclaim the usefulness as the water source of ultrapure water, then its water quality must and be selected from least one mode ground refinement treatment of following system and obtains the water source of ultrapure water through reverse osmosis, this system is to add ozone by ultraviolet ray, and ultraviolet ray adds H
2O
2, and the activated carbon adsorption mode forms.Preferably, this refinement treatment is that ultraviolet ray adds ozone.The dense row that the reverse-osmosis treated of this first recovery or discharge water produces holds waste water to process to remove the nitrate nitrogen of its middle and high concentration again with discharge of wastewater through the biological denitrification system; Perhaps when its nitrate nitrogen concentration is high, can partly not be directed to this NH yet
4F/F
-Waste water is processed its dilution is made it be fit to carry out this degassed/absorption.The reverse osmosis water that the reverse-osmosis treated of this first recovery or discharge water produces also can partly be directed to this NH
4F/F
-Waste water is processed its dilution is made it be fit to carry out this degassed/absorption.
Preferably, step c) the oxygen animalcule resolving system that has carries out in a sludge sump, more preferably, be provided with the sludge retention groove behind this sludge sump, for example, settling bath, monomer cut-off equipment and membrane biological reaction groove, wherein from step b) the waste water that is lowered of foreign matter content be detained for some time at this sludge sump and sludge retention groove, decompose so the residual impurity in the waste water is the Institute of Micro-biology in this mud in this residence time, and by this sludge retention groove discharge this first reclaim or discharge water simultaneously with sludge retention in this sludge retention groove.
This sludge retention groove is arranged at and is next to after the sludge sump, and the waste water that is flowed out by above-mentioned sludge sump is imported into this sludge retention groove.The some of the mud that is detained in this sludge retention groove is recycled and is used as step b) the some sources without oxygen animalcule mud without the oxygen animalcule is olation.
Description of drawings
Fig. 1 is that the present invention's comprehensive wastewater is processed blowdown system (discharge of wastewater) flow diagram.
Fig. 2 is that the present invention's comprehensive wastewater is processed blowdown system (discharge of wastewater) flow diagram.
Fig. 3 is the present invention's comprehensive wastewater recovery and processing system (water recovery) flow diagram.
Fig. 4 is the present invention's comprehensive wastewater recovery and processing system (water recovery) flow diagram.
Embodiment
If the present invention's treatment system is the usefulness of discharge of wastewater purpose, see Fig. 1, then mainly comprise a deoxidation agent system, a biological anaerobic/aerobic system, a degassed/absorption system, and one remove F
-System.The purpose of deoxidation agent system is to avoid oxygenant can reduce the activity of follow-up biology.This deoxidation agent system must look the kind of using oxygenant and difference is arranged: general oxygenant is to use hydrogen peroxide (H
2O
2), our result of test then can use reductive agent such as S-WAT (Na
2SO
3), sodium bisulfite (NaHSO
3), and Sodium Metabisulfite (Na
2S
2O
5) etc. dosing reduction, or with catalyst manganese dioxide, ferric oxide, activated carbon removal hydrogen peroxide; If use ozone water to be oxygenant, then the removal of this ozone water oxygenant can be used activated carbon, adds alkali and use ultraviolet ray to remove.
The part of above-mentioned biological aerobic system has the concentration of oxygen animalcule for increase, can use monomer, so that microorganism is gathered in the hole, increases the concentration of microorganism in the water biological pool; Another then can use membrane filtration and increase the concentration of microorganism in biological tank.Although native system name wastewater treatment blowdown system, the water after this biology anaerobic/aerobic system processes can discharge, and is also recyclable; And recoverable reason end is seen the use water quality of recovery point and decide.
NH
4F/F
-Waste water should use first degassed/absorption system to process.PH under alkaline state＞10, NH
4 +Mostly be under the molecular state, utilize degassed with NH
3From waste water, blow out removal.In this degas system, be used for absorbing NH
3The pharmaceutical chemicals of gas is phosphoric acid (H
3PO
4), sulfuric acid (H
2SO
4) or water, raw material or ammoniacal liquor that the product that generates can be used as fertilizer re-use.There is the processing water of some to introduce degassed/absorption system from the water side of biological anaerobic/aerobic system according to circumstances among Fig. 1, with dilution NH
4F/F
-Waste water make it be fit to the processing of this degassed/absorption system.Because degassed/absorption system treated water still contains the F of suitable concentration
-Ion is therefore need again through past F
-System processes.Remove F
-System can be reverse osmosis system or dosing (CaCl
2) treatment system, remove F
-The treated water of system can discharge and reclaim, and end is seen the demand that reclaims water quality.Other F in the technique
-Waste water also can remove F at this
-System handles together.If this removes F
-Reverse osmosis system is selected by system, and then the water outlet meeting of the dense row of this reverse osmosis system (concentrate discharge) end is according to circumstances and by dosing (CaCl
2) process, avoid F
-The environmental regulation that the ion discharging is too high.
As shown in Figure 2, if can collect separately when the contamination level of ammonia nitrogen waste water is large, and use degassed/absorption system individual curing it, import again biological anaerobic/aerobic system.If the contamination level of ammonia nitrogen waste water hour then can directly import biological anaerobic/aerobic system.If can collect separately when the contamination level of TMAH waste water is large, and the biological anaerobic/aerobic system that imports again of use bio anaerobic system individual curing.If the contamination level of TMAH waste water hour then can directly import biological anaerobic/aerobic system.
If the water outlet of processing through this biology anaerobic/aerobic system is will be used as the front end of ultrapure water as the water source, then its water quality must be through processing further, after being included in this anaerobic/aerobic system and processing, connects a reverse osmosis system, adds a refining system.This refining system can be AOP, comprises that ultraviolet ray adds ozonation system or ultraviolet ray adds H
2O
2System; And optionally an activated carbon device places at last again.See Fig. 3, Fig. 4 flow diagram.This reverse osmosis system according to circumstances water of its concentrated end is admitted to the nitrate nitrogen that a biological denitrating system processes to remove its middle and high concentration.If the not high waste water of also can according to circumstances the dense row of this reverse osmosis system being held of nitrate nitrogen concentration is incorporated into this NH of processing
4F/F
-Waste water degassed/absorption system, with the dilution NH
4F/F
-Waste water make it be fit to the processing of this degassed/absorption system.The going out flowing water and also can be introduced in according to circumstances and process this NH of this reverse osmosis system
4F/F
-Waste water degassed/absorption system, with the dilution NH
4F/F
-Waste water make it be fit to the processing of this degassed/absorption system.
The present invention will use lower embodiment and further be understood, and this embodiment but not is used for the restriction scope of the invention as illustrative purposes only.
Embodiment
Embodiment 1: deoxidation agent system testing
1.H
2O
2Remove test data with the dosing S-WAT
Test with operate continuously, the waste strength of influent stream sees Table 2.Mould factory testing process and operating parameters: dosing S-WAT, chemical feeding quantity are 1.2 times of theoretical value, so that H
2O
2Be down to＜5ppm (200 hours test durations).The water quality explanation was such as table 2 after deoxidation agent system processed.
Table 2, H
2O
2Remove test data with the dosing S-WAT
Can find out that by the data of table 2 the deoxidation agent system of dosing can be used to this complicacy waste water and effectively remove H
2O
2Oxygenant.
2.H
2O
2Remove test data with catalyzer
A. with MnO
2Test
Test with operate continuously, the waste strength of feed-water end sees Table 3.Mould factory testing process and operating parameters: with MnO
2As catalyst test, 5 minutes residence time, 200 hours test durations are so that H
2O
2Be down to＜5ppm, water quality illustrates such as table 3.
Table 3, H
2O
2With catalyzer MnO
2Remove test data
Data by table 3 can be found out with MnO
2The deoxidation agent system that makes catalyzer can be used to the waste water of this shunting and effectively remove H
2O
2Oxygenant.
B. test with activated carbon
Test with operate continuously, the waste strength of feed-water end sees Table 4.Mould factory testing process and operating parameters: as catalyst test, 5 minutes residence time, 200 hours test durations are so that H with activated carbon
2O
2Be down to＜5ppm, water quality illustrates such as table 4.
Table 4, H
2O
2With catalyst activity carbon removal test data
Can be found out by the data of table 4 can quilt with the deoxidation agent system of activated carbon catalyst
The waste water that is used for this shunting is removed H effectively
2O
2Oxygenant.
3. oxidant, ozone water is removed test data
A. add alkali and remove test
10% (w/w) 200l/h ozone gas flow is injected ultrapure water, and its flow velocity is 100l/h, and the pressure of ozone maintains 1.5Bar, simulates the generation of upstream ozone water with this.Utilize the change of pH so that the change in concentration of ozone.When pH when being transferred to the meta-alkali condition, the concentration of ozone water can significantly reduce, therefore can with this removal method that is used as the ozone water oxygenant, see Table 5.
Table 5, oxidant, ozone water add alkali and remove test data
| pH | O 3Concentration (ppm) |
| 4 | 26 |
| 4.5 | 26.5 |
| 5 | 22 |
| 5.5 | 17 |
| 6 | 16 |
| 6.5 | 12 |
| 7 | 8 |
| 7.5 | 1.5 |
| 8 | 1.8 |
| 8.5 | 3.9 |
| 9 | 3.8 |
| 9.5 | 3.5 |
| 10 | 2.0 |
B. test is removed in ultraviolet ray
For the consistency of ozone water of high density, the uv reactor of pressing during we select is reacted it.The ozone water of simulation produces in the mode of above-mentioned a, and concentration is at 25ppm; In 2.4kw, press ultraviolet ray, flow velocity 3T/h, 18 seconds residence time, the concentration of ozone can be down to less than 2ppm.
Embodiment 2: the flow testing of deoxidation agent system, biological aerobic/anaerobic system and reverse osmosis system
1. deoxidation agent system+biological aerobic system (testing with monomer) test data
Test with operate continuously, the waste strength of feed-water end sees Table 6.Mould factory testing process and operating parameters: pass through first the dosing S-WAT, so that H
2O
2Be down to＜40ppm, and adjust pH value to 6.8; In the biological aerobic groove monomer (12 hours residence time) is arranged.Water quality such as table 6 after biological aerobic groove is processed.
Table 6, deoxidation agent system+biological aerobic system (testing with monomer) test data
2. deoxidation agent system+biological anaerobic/aerobic system (testing with microbial film)+reverse osmosis system test data
Test with operate continuously, the waste strength of influent stream sees Table 7.Mould factory testing process and operating parameters: pass through first the dosing S-WAT, so that H
2O
2Be down to＜40ppm, and adjust pH value to 11.3; Biological anaerobic groove (2.5 hours residence time); Biological aerobic groove adds membrane filtration module (10 hours residence time); Pass through again reverse osmosis system.Processing unit membrane filtration module is processed rear water quality, is reached the water side water quality explanation of reverse osmosis system such as table 7.
Table 7, deoxidation agent system+biological anaerobic/aerobic system (testing with the membrane filtration module)+reverse osmosis system test data
Under this holonomic system combination, the concentration of water quality such as IPA and acetone was respectively the ppb less than units after the membrane filtration module was processed, much smaller than the requirement＜3ppm of environmental regulation; COD water quality is also at units ppm; Ammonia nitrogen is also fully removed from waste water, and its concentration levels off to zero.Therefore, its impurity concentration of water outlet that had both made dense row's end of reverse osmosis is 4 to 6 times of influent concentration, and its IPA, acetone and ammonia nitrogen concentration also are to level off to zero.With TOC, the effluent quality of reverse osmosis system and Xinzhu City tap water quality are made comparisons, excellent 3～6 times of its water-quality ratio tap water simultaneously; This water quality can feel at ease can improve the rate of utilization of water as the water source of ultrapure water.Hence one can see that, and the inventive method/system can with the semiconductor technology wastewater treatment to a certain degree so that waste water can reclaim use, also can make the discharging of factory meet more harsh environmental regulation requirement simultaneously.
3. System integration property testing
Priority interdependency between main test deoxidation agent system and the biological anaerobic/aerobic system.In above-mentioned deoxidation agent system+biological anaerobic/aerobic system (testing with the membrane filtration module)+reverse osmosis system test, after system stability produces water such as above-mentioned data, the dosing of cut deoxidation agent system.After three days, NH
4 +-N data liter is back to 93.5ppm, and expression is when oxygenant exists, and the ammonia nitrogen bacterium can come to harm; After 7 days, the effluent quality COD after biological anaerobic/aerobic system rises to 100ppm, and expression is when the oxygenant sustainable existence, and the bacterium of practising take organism as food also can come to harm.The oxidation system of dieing has its necessity, and must remove oxygenant before in biosystem and carry out certain processing.
Embodiment 3: degassed/the absorption system test
Test with operate continuously, the waste strength of feed-water end sees Table 8.Model factory testing process and operating parameters: at first waste water is adjusted pH value to 11.5 in a pH groove, then import a degassing vessel in wherein take air the discharge ratio being blown the retention time of sewage of degassing vessel 1.2 hours as 1000: 1 ratio by the bottom.NH
4The ammonia nitrogen degassing efficiency of OH waste water is 80%.The effluent quality explanation is such as table 8.Be admitted to an absorption cell by the liquid level air that contains ammonia out, with phosphate aqueous solution absorption ammonia (product ammonium phosphate) wherein.
Table 8, degassed/the absorption system test
Table 8 data declaration other species in this waste water can't play draw with the molecule of ammonia nitrogen and reduce degassing efficiency.
Embodiment 4: the refining system test
1.AOP (the UV/O of system
3) the removal testing efficiency
Test with operate continuously, water quality saw Table 9 after the reverse osmosis system of influent stream was processed.Mould factory testing process and operating parameters: ozone concn 2ppm; 2.4kw middle pressure ultraviolet ray; Flow velocity 3T/h; 18 seconds residence time; Reflux ratio 5: 1, going out flowing water water quality TOC has 70% efficient, and water quality illustrates such as table 9.
Testing efficiency is removed by table 9, AOP system (UV/O3)
Embodiment 5: the bio anaerobic system testing
The present embodiment carries out the bio anaerobic of TMAH waste water to be processed.Test with operate continuously, the TMAH waste strength 136ppm of feed-water end, it is imported into the bottom of a biological anaerobism groove, is detained in this groove and decomposes its contained organism through anaerobe wherein in 24 hours.The anaerobic oxidation reduction potential is-200 to-500Mv.Decomposition efficiency is 60%.
Claims (16)
1. the treatment process of a semiconductor technology waste water comprises the following step:
A) will be compiled by several strands of semiconductor technology waste water and form the comprehensive wastewater that contains oxygenant, organic impurities and inorganics impurity and carry out the deoxidation agent and process, this comprehensive wastewater does not contain in fact NH
4F/F
-Waste water;
B) to process the waste water that is lowered from step oxygenate content a) without the oxygen animalcule is olation, so that wherein contained impurity partly decomposes; And
C) there to be the oxygen animalcule is olation to process from step b) the waste water that is lowered of foreign matter content so that the impurity that residues in is wherein further decomposed, reclaim or discharge water and obtain one first.
2. the method for claim 1, it further comprises NH
4OH wastewater eluting or TMAH gold-tinted processing wastewater carry out individual treated, wherein
This NH
4The OH wastewater eluting is carried out a degassed/absorption and processes, and it comprises adjusts NH
4The pH value of OH waste water is extremely more than or equal to 10; Continue to aerating wastewater for some time, so from waste water, blow out NH
3, and obtain the first part processing water that ammonia-nitrogen content reduces; And will include from the gas importing one that liquid level is emerged the air-breathing district of absorption agent, so with NH contained in the gas
3Be absorbed on this absorption agent;
This TMAH gold-tinted processing wastewater is carried out a biological anaerobic treatment, comprise this TMAH gold-tinted processing wastewater is imported a biological anaerobism groove, and be stranded in wherein 5-48 hour and TMAH is decomposed by anaerobion wherein, process water and discharge one second part, wherein the redox potential of the waste water in this groove is-200 to-500mV;
This first part is processed water and the second part and is processed water and together carried out step b by the waste water merging that the oxygenate content that a) flows out with above-mentioned steps is lowered) and c).
3. the method for claim 1, it further comprises NH
4OH wastewater eluting or TMAH gold-tinted processing wastewater are processed, wherein
This NH
4The waste water that the OH wastewater eluting is lowered by the oxygenate content that a) flows out with above-mentioned steps merge together carry out step b) and c);
The waste water that this TMAH gold-tinted processing wastewater is lowered by the oxygenate content that a) flows out with above-mentioned steps merge together carry out step b) and c).
4. method as claimed in claim 2, it further comprises NH
4F/F
-Waste water is processed, wherein,
This NH
4F/F
-Waste water is carried out a degassed/absorption and processes, and comprises and adjusts NH
4F/F
-The pH value of waste water is extremely more than or equal to 10; Continue to aerating wastewater for some time, so from waste water, blow out NH
3To include from the gas importing one that liquid level is emerged the air-breathing district of absorption agent, so with NH contained in the gas
3Be absorbed on this absorption agent; The waste water of sloughing the part ammonia nitrogen then is carried out F
-Process, comprise reverse osmosis or add CaCl
2, reclaim or discharge water and obtain one second.
5. method as claimed in claim 4, wherein,
If F
-Concentration＞400ppm, then this removes F
-Processing comprises and adds CaCl
2, produce CaF
2Precipitation; Solid-liquid separation, directly CaF is removed in discharging
2The waste water of precipitation, at this moment its F
-Concentration＜15ppm;
If F
-Concentration is not more than 400ppm, and then this removes F
-Processing comprises reverse-osmosis treated, and the reverse osmosis water that obtains is regarded as one the 3rd and reclaims or discharge water, and produce contain F
-The reverse osmosis concentrated row of ion holds waste water then by adding CaCl
2Mode is removed F wherein
-Ion is discharged again.
6. method as claimed in claim 4, wherein other contains F in this semiconductor technology
-Waste water and this waste water of sloughing ammonia nitrogen together carry out this and remove F
-Process.
7. method as claimed in claim 4 is wherein by above-mentioned steps c) flow out first reclaim or discharge water be used for diluting this NH by the shunting some
4F/F
-Waste water makes it be fit to carry out this degassed/absorption and processes.
8. such as claim 2 or 4 described methods, NH wherein
3Absorption agent is phosphoric acid, sulfuric acid or water.
9. such as claim 1 or 4 described methods, it further comprises step c) flow out first reclaim or discharge water through a reverse-osmosis treated; And follow the refinement treatment that process is selected from least one mode of following system, and this system is to add ozone by ultraviolet ray, ultraviolet ray adds H
2O
2, and the activated carbon adsorption mode forms.
10. method as claimed in claim 9, wherein this refinement treatment is that ultraviolet ray adds ozone.
11. method as claimed in claim 9, wherein this first reclaims or dense row that the reverse-osmosis treated of discharge water produces holds waste water to be carried out biological denitrification to process to remove the nitrate nitrogen of its middle and high concentration again with discharge of wastewater; Perhaps when its nitrate nitrogen concentration was not high, its part was directed to this NH
4F/F
-Waste water is processed its dilution is made it be fit to carry out this degassed/absorption.
12. method as claimed in claim 9, the reverse osmosis water part that the reverse-osmosis treated of this first recovery or discharge water produces is directed to this NH
4F/F
-Waste water is processed its dilution is made it be fit to carry out this degassed/absorption.
13. method as claimed in claim 5 wherein the 3rd reclaims or discharge water is imported into a refining system and reclaims.
14. the method for claim 1, wherein step c) the oxygen animalcule resolving system that has in a sludge sump, carry out.
15. method as claimed in claim 14, wherein be provided with the sludge retention groove behind this sludge sump, wherein from step b) the waste water that is lowered of foreign matter content be detained for some time at this sludge sump and sludge retention groove, decompose so the residual impurity in the waste water is the Institute of Micro-biology in this mud in this residence time, and by this sludge retention groove discharge this first reclaim or discharge water simultaneously with sludge retention in this sludge retention groove.
16. method as claimed in claim 15, the some of the mud that wherein is detained in this this sludge retention groove is recycled and is used as step b) the some sources without oxygen animalcule mud without the oxygen animalcule is olation.
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| TW100134476 | 2011-09-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI507365B (en) * | 2014-01-03 | 2015-11-11 | Selective Oxidation of High Concentration Ammonia Nitrogen Wastewater by Catalyst | |
| CN111386246A (en) * | 2017-11-23 | 2020-07-07 | 诺力昂化学品国际有限公司 | Process for treating phosphite containing waste streams |
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| TW201420517A (en) | 2013-09-17 | 2014-06-01 | Leaderman & Associates Co Ltd | Method and device for processing waste water containing TMAH and ammonium nitrogen |
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| CN101759320A (en) * | 2008-12-26 | 2010-06-30 | 财团法人工业技术研究院 | Treating system and method of ammonia nitrogen wastewater |
| CN101798155A (en) * | 2009-02-09 | 2010-08-11 | 财团法人工业技术研究院 | Treatment system and method of ammonia nitrogen sewage |
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| TWI284117B (en) * | 2004-12-09 | 2007-07-21 | Ind Tech Res Inst | Method and system for treating wastewater containing hydrogen peroxide |
| JP2007069199A (en) * | 2005-08-09 | 2007-03-22 | Sanyo Electric Co Ltd | Apparatus for treating water |
| TWI365173B (en) * | 2008-05-06 | 2012-06-01 | cheng fang Lin | Treating unit for simultaneous removal of carbon and nitrogen from wastewater and treating apparatus having the same |
-
2011
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| CN101759320A (en) * | 2008-12-26 | 2010-06-30 | 财团法人工业技术研究院 | Treating system and method of ammonia nitrogen wastewater |
| CN101798155A (en) * | 2009-02-09 | 2010-08-11 | 财团法人工业技术研究院 | Treatment system and method of ammonia nitrogen sewage |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI507365B (en) * | 2014-01-03 | 2015-11-11 | Selective Oxidation of High Concentration Ammonia Nitrogen Wastewater by Catalyst | |
| CN111386246A (en) * | 2017-11-23 | 2020-07-07 | 诺力昂化学品国际有限公司 | Process for treating phosphite containing waste streams |
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