EP2054350A2 - Methods and systems for biological treatment of flue gas desulfurization wastewater - Google Patents
Methods and systems for biological treatment of flue gas desulfurization wastewaterInfo
- Publication number
- EP2054350A2 EP2054350A2 EP07811473A EP07811473A EP2054350A2 EP 2054350 A2 EP2054350 A2 EP 2054350A2 EP 07811473 A EP07811473 A EP 07811473A EP 07811473 A EP07811473 A EP 07811473A EP 2054350 A2 EP2054350 A2 EP 2054350A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- wastewater
- reactor
- fgd
- introducing
- flue gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000003546 flue gas Substances 0.000 title claims abstract description 48
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000011282 treatment Methods 0.000 title claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 title description 3
- 230000023556 desulfurization Effects 0.000 title description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 47
- 239000006096 absorbing agent Substances 0.000 claims abstract description 46
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 29
- 150000007524 organic acids Chemical class 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 230000003750 conditioning effect Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 43
- 239000011669 selenium Substances 0.000 claims description 40
- 229910052711 selenium Inorganic materials 0.000 claims description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 235000015097 nutrients Nutrition 0.000 claims description 6
- 229940082569 selenite Drugs 0.000 claims description 6
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 claims description 6
- 235000000346 sugar Nutrition 0.000 claims description 6
- 230000000153 supplemental effect Effects 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 8
- 235000011054 acetic acid Nutrition 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 4
- 239000001361 adipic acid Substances 0.000 claims 4
- 235000011037 adipic acid Nutrition 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 4
- 238000004064 recycling Methods 0.000 claims 4
- 229910052716 thallium Inorganic materials 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 22
- 239000010802 sludge Substances 0.000 description 16
- 230000009467 reduction Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000002699 waste material Substances 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 241000894007 species Species 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000011785 micronutrient Substances 0.000 description 3
- 235000013369 micronutrients Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910018143 SeO3 Inorganic materials 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000021112 essential micronutrients Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000021073 macronutrients Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003957 organoselenium compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- CRDYSYOERSZTHZ-UHFFFAOYSA-N selenocyanic acid Chemical group [SeH]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011269 treatment regimen Methods 0.000 description 1
- -1 waste sugar Chemical compound 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/04—Oxidation reduction potential [ORP]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- This disclosure relates to wastewater treatment methods and systems that remove organic and inorganic pollutants captured in the purge stream from air pollution control equipment.
- Flue Gas Desulfurization (FGD) process wastewater contains elevated levels of chlorides; significant concentrations of heavy metal contaminants such as chromium, mercury, and selenium; often high levels of nitrates; and a very high solids content that consists primarily of calcium sulfate, calcium carbonate, magnesium hydroxide, and fly ash.
- FGD wastewater contains elevated levels of chlorides; significant concentrations of heavy metal contaminants such as chromium, mercury, and selenium; often high levels of nitrates; and a very high solids content that consists primarily of calcium sulfate, calcium carbonate, magnesium hydroxide, and fly ash.
- Treatment of FGD wastewater is a significant need for utility operations. Physical / chemical treatment processes are typically used for neutralization and calcium sulfate desaturation, removal of some heavy metals, clarification and sludge thickening.
- conventional chemical precipitation techniques do not reliably eliminate heavy metal contaminants such as selenium and hexavalent chromium below outfall discharge
- FGD process wastewater is the focus of increasingly stringent effluent requirements, with outfall discharge standards (monthly average and daily maximum) typically established for:
- Heavy Metals including but not limited to Arsenic, Chromium, Copper, Mercury & Selenium
- Selenium is an essential micronutrient for animals and bacteria. However, it becomes highly toxic when present above minute concentrations.
- the oxidized species of selenium, selenate (Se Vl) and selenite (Se IV) are highly soluble and bioavailable, whereas reduced forms are insoluble and much less bioavailable.
- Regulatory limits for soluble selenium remain variable with targets ranging from 800 ug/L down to the U.S. national drinking water standard of 50 ug/L, frequently depending upon the discharge receiving water body.
- Selenium exists in multiple valence states in the natural environment and the impact of selenium speciation on treatment efficiency is known.
- Selenium in the form of Selenite (Se IV; SeO 3 ) can be removed with 65 to 85% efficiency using physical-chemical treatment approaches while Selenate (Se Vl; SeO 4 ) removal efficiency is limited to ⁇ 10% with physical- chemical treatment.
- a method of treating flue gas and wastewater generated by treating the flue gas includes: introducing the flue gas and an organic acid conditioning agent into a wet-oxidation scrubber/absorber substantially to remove sulfur dioxide from the flue gas and condition resulting FGD wastewater for downstream biological treatment; introducing FGD scrubber wastewater generated by the absorber into an anoxic biological reactor to substantially denitrify and/or reduce selected heavy metals in the FGD scrubber wastewater; and introducing substantially denitrified wastewater into an anaerobic biological reactor to substantially reduce the amount of sulfate and/or selected heavy metals in the FGD scrubber wastewater.
- a system for treating flue gas and wastewater generated by treating the flue gas includes: a wet-oxidation scrubber/absorber comprising a flue gas inlet, a flue gas treatment fluid inlet, an organic acid conditioning agent inlet, and a wastewater outlet; an anoxic reactor located downstream of the wet-oxidation scrubber/absorber to substantially denitrify FGD scrubber wastewater generated by the absorber; and an anaerobic reactor located downstream of the anoxic reactor to substantially reduce the amount of sulfate and/or selected heavy metals in the FGD scrubber wastewater.
- a method of treating FGD scrubber wastewater includes: introducing FGD scrubber wastewater generated by combining flue gas and an organic acid conditioning agent in a wet-oxidation scrubber/absorber into an anoxic reactor to substantially denitrify the FGD scrubber wastewater; and introducing substantially denitrified wastewater into an anaerobic reactor to reduce the amount of sulfate and/or selected heavy metals in the FGD scrubber wastewater.
- a system for treating FGD scrubber wastewater includes: an anoxic biological reactor located downstream of a wet- oxidation scrubber/absorber to substantially denitrify FGD scrubber wastewater generated by the absorber; and an anaerobic biological reactor located downstream of the anoxic reactor to substantially reduce the amount of sulfate and/or selected heavy metals in the FGD scrubber wastewater.
- FIG. 1 is a schematic diagram of a representative process flow for a wet-oxidation scrubber/absorber system and associated conventional FGD wastewater treatment system.
- FIG. 2 is a schematic flow diagram of a representative biological treatment system for FGD scrubber wastewater.
- This disclosure relates to biological treatment systems for FGD scrubber wastewater, encompassing the feed of a pure organic acid conditioning reagent, such as formic acid, to the wet-oxidation scrubber / absorber and later followed by a combination of anoxic, anaerobic and aerobic staged activated sludge reactors and associated clarification systems for removal of TN 1 reduction and precipitation of heavy metals and elimination of suspended solids from the FGD purge stream.
- a pure organic acid conditioning reagent such as formic acid
- This disclosure also relates to processes for biological treatment of
- FGD scrubber wastewater particularly to treatments that improve the removal efficiency of TN and heavy metals including but not limited to selenium.
- the treatment system 10 includes a line 12 to add a pure organic acid conditioning reagent, such as formic acid, to absorber 14 as indicated in Fig. 1.
- a pure organic acid conditioning reagent such as formic acid
- the absorber 14 also connects to a particle scrubber 16 and a recirculation tank 18.
- the recirculation tank 18 directly receives flue gas treatment fluid through supply line 20 which is indirectly supplied into absorber
- Flue gas treatment fluid may comprise, among other things, a lime/limestone water slurry.
- FGD scrubber wastewater exits absorber 14 through line 32 and enters recirculation tank 18. Selected portions of FGD scrubber wastewater exit through recirculation tank 18 and may proceed to clarifier 34. This may be followed by passage of the clarified wastewater to holding tank 36. Wastewater contained in holding tank 36 can be recycled to recirculation tank 18 by way of line 38. The partially dewatered sludge may be channeled from clarifier 34 to vacuum filter 40 by way of line 42, where most of the remaining water is removed. The waste sludge can then be sent to a settling pond or landfill 44.
- FGD scrubber wastewater may also flow from clarifier 34 to additional treatment systems such as a biological treatment system of Fig. 2 by way of line 46 and as activated by valve 47.
- FIG. 2 a selected, representative biological treatment system 48 for FGD scrubber wastewater is shown in a schematic form.
- the system 48 includes an inlet 50, a staged suspended growth biological reactor 52 comprising anoxic 54 and anaerobic 56 zones, an intermediate clarifier 58, an aerobic suspended growth biological reactor 60, a final clarifier 62, a storage tank 64 and a filtration stage 76.
- the biological treatment system 48 of Fig. 2 can perform the following functions:
- the biological treatment system 48 may receive influent feed from an upstream physical-chemical treatment system such as from clarifier 34, for example, of Fig. 1 , in the form of deoxygenated FGD purge wastewater.
- the biological reactors of the system 48 may include completely mixed, continuous flow, activated sludge reactors.
- the first cell (or reactor 54) in the system 48 is the anoxic stage, where nitrates are reduced to nitrogen gas via denitrification reactions.
- FGD wastewater is deficient in macronutrients, including ammonia nitrogen and orthophosphorous, as well as many of the micronutrients required to support biological growth, there is a process requirement for supplemental nutrient addition to yield efficient treatment performance.
- Reactor 54 is thus fed with a biodegradable nutrient blend, containing macro- and micronutrients to maintain microbial growth.
- Nutrients include but are not limited to supplemental carbon such as waste sugar, corn syrup, molasses or the like, urea or the like to provide ammonia nitrogen, phosphoric acid, micronutrients and yeast extract to provide necessary trace metals and growth factors. Fermentation of sugars dosed into the anoxic reactor 54 results in the conversion of sucrose to volatile fatty acids (VFAs) that sulfate / selenium reducing microorganisms are capable of metabolizing efficiently in the downstream anaerobic reactor stage(s). Additional carbon sources such as lactate, acetate or the like may also be added directly to the anoxic/anaerobic reactors to enhance selenium removal by enriching the selenium reducing microorganisms.
- VFAs volatile fatty acids
- Additional carbon sources such as lactate, acetate or the like may also be added directly to the anoxic/anaerobic reactors to enhance selenium removal by enriching the selenium reducing microorganisms.
- a pure organic acid stream such as formic acid
- line 12 of absorber 14 provides a means to introduce a biodegradeable carbon substrate to the wastewater that can provide COD to the system for downstream biological removal of nitrates and selected heavy metals.
- a dosage of 200 mg/L formate equates to a theoretical COD dosage of about 70 mg/L.
- the anoxic / anaerobic biological reactor 52 may be an overflow, under-flow weir design which mimics a plug-flow system without the need to incorporate separate reactor tanks that are physically isolated from one another. Other configurations / structures may be used as appropriate.
- Operational inputs for successful treatment involve targeting the appropriate oxidation-reduction potential (ORP) in the various reactor stages.
- ORP oxidation-reduction potential
- the anoxic reactor 54 may preferably be maintained in the range of about -50 to about -300 mV to yield efficient denitrification.
- the role of the anoxic denitrification reactor 54 is important. We found that efficient removal of selected heavy metals such as selenium substantially depends upon sequential substrate removal, specifically the prior elimination of nitrates.
- organo- selenium complexes were found to be surprisingly recalcitrant to selenium reduction by the microbial population in downstream biological reactors.
- use of a pure organic acid reagent, such as formic acid, to improve SO 2 removal efficiency at the scrubber further provides downstream advantages by yielding a wastewater matrix that could readily be treated for selenium removal.
- the staged biological reactors create a reducing environment for the conversion of selenate or selenite to elemental selenium, which precipitates out of solution into the wastewater solids.
- the partially treated FGD wastewater leaves the anoxic reactor 54 substantially devoid of nitrate contamination and flows into the next cell (i.e., the anaerobic reactor 56), which in one aspect may be operated at an ORP in the range of about -200 to about -500 mV, where sulfate and heavy metal- reducing organisms begin to remove sulfates and the selected heavy metals from the wastewater.
- the treated water then flows to an optional third cell (anaerobic reactor stage) to ensure that heavy metals are removed to levels allowing outfall discharge permits to be met.
- the treated effluent from the anoxic / anaerobic biological reactors 54 / 56 may flow into a mix chamber allowing for chemical addition to improve downstream sedimentation within the intermediate clarifier 58. From the mix chamber of the anoxic / anaerobic reactors 54 / 56, the treated effluent flows into a settling type intermediate clarifier 58, where TSS is settled out and the clarifier underflow solids are recycled to the anoxic reactor 54 by lines 66 and 68 as return activated sludge (RAS) or sent to a sludge holding tank (not shown) by line 70 as waste activated sludge (WAS).
- RAS return activated sludge
- WAS waste activated sludge
- the partially treated FGD wastewater flows into the aerobic biological reactor 60 for removal of BOD and ammonia.
- the aerobic biological reactor 60 includes operation at positive ORP.
- the FGD wastewater flows into a settling type final clarifier 62, where TSS is settled out and clarifier underflow solids may be recycled to the head of the aerobic reactor 62 by lines 72 and 74 as return activated sludge (RAS) or sent to a sludge holding tank (not shown) by line 70 as waste activated sludge (WAS).
- RAS return activated sludge
- WAS waste activated sludge
- the clarified water flows into a wet effluent well / tank 64 for pumping to pressure filters 76 and ultimately discharge to the environment.
- the filters may be gravity sand, multimedia or the like type filters.
- Powdered Activated Carbon (PAC) or other adsorbent materials such as charred poultry waste or the like added to the anaerobic and/or aerobic biological reactor will also adsorb any remaining organo-selenium complexes to assist reaching a final effluent selenium concentration that is below about 200 ⁇ g/L.
- PAC can be added at a dosage of about 550 ppm, for example.
- a biological treatment system comprising of a 2-stage, completely mixed, anaerobic activated sludge reactor having a total reactor volume of approximately 2,000 gallons followed by a 500-gallon clarifier and an aerobic activated sludge reactor and final clarifier was fabricated and installed on a sidestream of FGD scrubber blowdown at an operating power generating station.
- the facility initiated pure organic acid addition in the form of formic acid to the absorber to enhance the downstream biological treatment process while continuing to provide SO 2 removal at the wet-oxidation scrubber/absorber.
- the use of a pure organic acid feed resulted in significant reductions in the levels of complexed selenium present. Subsequently, this resulted in improved treatability of the FGD wastewater with the performance of the biological treatment system greatly enhanced as noted below.
- staged activated sludge design was found to yield substantially complete denitrification of influent FGD scrubber wastewater under anoxic conditions, consistently achieving effluent NO 3 -N concentrations below 1 mg/L for influent nitrate levels ranging from 200 to 600 mg/L.
- the aerobic reactor performance was found to be much less sensitive to changes in the influent soluble selenium concentration allowing for quick adaptation to system upsets that result in rapid increase in influent Se levels.
- the complexity of Selenium speciation within FGD scrubber wastewaters may be reduced or eliminated by feeding a pure organic acid conditioning additive, such as formic acid, to the wet-oxidation scrubber/absorber. Subsequently, this approach improves downstream biological treatment while maintaining SO 2 removal efficiency at the absorber.
- a pure organic acid conditioning additive such as formic acid
- Reactors are seeded with biomass from natural microbial populations avoiding the need to regularly add "specialized" microbial cultures and thereby reducing annual operational costs.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84008406P | 2006-08-25 | 2006-08-25 | |
| PCT/US2007/018552 WO2008027259A2 (en) | 2006-08-25 | 2007-08-22 | Methods and systems for biological treatment of flue gas desulfurization wastewater |
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| EP07811473A Ceased EP2054350A2 (en) | 2006-08-25 | 2007-08-22 | Methods and systems for biological treatment of flue gas desulfurization wastewater |
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| Country | Link |
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| EP (1) | EP2054350A2 (en) |
| CA (1) | CA2661739A1 (en) |
| WO (1) | WO2008027259A2 (en) |
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| US8557118B2 (en) * | 2010-02-02 | 2013-10-15 | General Electric Company | Gasification grey water treatment systems |
| US20120024798A1 (en) * | 2010-07-27 | 2012-02-02 | Timothy Michael Pickett | Selenium Removal Using Chemical Oxidation and Biological Reduction |
| CN103739065A (en) * | 2013-12-04 | 2014-04-23 | 吉林省电力科学研究院有限公司 | Anaerobic biological treatment method of heat-engine plant desulphurization waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308509A (en) * | 1993-03-08 | 1994-05-03 | The Babcock & Wilcox Company | FGD performance enhancement by hydroclone and recycling steps |
| US5433936A (en) * | 1992-03-11 | 1995-07-18 | Mitsubishi Jukogyo Kabushiki Kaisha | Flue gas desulfurization process |
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| JPS59173199A (en) * | 1983-03-22 | 1984-10-01 | Kansai Electric Power Co Inc:The | Biological treatment of waste water containing dithionic acid and ammonia |
| CZ292547B6 (en) * | 1995-02-06 | 2003-10-15 | Biostar Development C. V. | Process for purifying flue gas containing nitrogen oxides and apparatus for purification flue gas |
| JP3658802B2 (en) * | 1995-06-23 | 2005-06-08 | 栗田工業株式会社 | Method for treating selenium-containing water |
| EP0769479A1 (en) * | 1995-10-18 | 1997-04-23 | N.V. Kema | Process for cleaning a waste water stream or the like |
| JP2006205097A (en) * | 2005-01-31 | 2006-08-10 | Mitsubishi Heavy Ind Ltd | Biological treatment method of wastewater |
| WO2007012181A1 (en) * | 2005-07-25 | 2007-02-01 | Zenon Technology Partnership | Apparatus and method for treating fgd blowdown or similar liquids |
-
2007
- 2007-08-22 EP EP07811473A patent/EP2054350A2/en not_active Ceased
- 2007-08-22 WO PCT/US2007/018552 patent/WO2008027259A2/en not_active Ceased
- 2007-08-22 CA CA 2661739 patent/CA2661739A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433936A (en) * | 1992-03-11 | 1995-07-18 | Mitsubishi Jukogyo Kabushiki Kaisha | Flue gas desulfurization process |
| US5308509A (en) * | 1993-03-08 | 1994-05-03 | The Babcock & Wilcox Company | FGD performance enhancement by hydroclone and recycling steps |
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| CA2661739A1 (en) | 2008-03-06 |
| WO2008027259A3 (en) | 2009-07-09 |
| WO2008027259A2 (en) | 2008-03-06 |
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