WO2013063727A1 - Process for increasing activity of nitrification microorganism in active sludge by in-situ preparation and addition of iron hydroxide - Google Patents
Process for increasing activity of nitrification microorganism in active sludge by in-situ preparation and addition of iron hydroxide Download PDFInfo
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- WO2013063727A1 WO2013063727A1 PCT/CN2011/001984 CN2011001984W WO2013063727A1 WO 2013063727 A1 WO2013063727 A1 WO 2013063727A1 CN 2011001984 W CN2011001984 W CN 2011001984W WO 2013063727 A1 WO2013063727 A1 WO 2013063727A1
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- WIPO (PCT)
- Prior art keywords
- iron
- activated sludge
- ultrafine
- solution
- nitrification
- Prior art date
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- 239000010802 sludge Substances 0.000 title claims abstract description 88
- 244000005700 microbiome Species 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 235000014413 iron hydroxide Nutrition 0.000 title claims abstract description 43
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 title abstract description 5
- 230000001965 increasing effect Effects 0.000 title abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 52
- 230000000694 effects Effects 0.000 claims abstract description 32
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 27
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 26
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 150000002505 iron Chemical class 0.000 claims abstract description 10
- 230000007774 longterm Effects 0.000 claims abstract description 8
- 239000013589 supplement Substances 0.000 claims abstract description 7
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 6
- 239000010865 sewage Substances 0.000 claims description 47
- 230000001546 nitrifying effect Effects 0.000 claims description 35
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 229960004887 ferric hydroxide Drugs 0.000 claims description 17
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 17
- 230000000813 microbial effect Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- -1 iron ions Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 238000005842 biochemical reaction Methods 0.000 claims description 7
- 230000002503 metabolic effect Effects 0.000 claims description 6
- 102000004190 Enzymes Human genes 0.000 claims description 5
- 108090000790 Enzymes Proteins 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- 230000001580 bacterial effect Effects 0.000 claims description 4
- 238000006911 enzymatic reaction Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000028327 secretion Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006757 chemical reactions by type Methods 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims 2
- 230000007269 microbial metabolism Effects 0.000 claims 1
- 238000012258 culturing Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 97
- 229910052757 nitrogen Inorganic materials 0.000 description 48
- 239000000243 solution Substances 0.000 description 37
- 241000894006 Bacteria Species 0.000 description 12
- 230000009471 action Effects 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004060 metabolic process Effects 0.000 description 4
- 238000009629 microbiological culture Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000729 antidote Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000037149 energy metabolism Effects 0.000 description 1
- 229940125532 enzyme inhibitor Drugs 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006241 metabolic reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- 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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1205—Particular type of activated sludge processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Definitions
- the invention relates to a method for improving the nitrification ability of nitrifying microorganisms in activated sludge for biological denitrification treatment of sewage under low temperature conditions, and belongs to the technical field of sewage treatment.
- the activated sludge process is a biological treatment method for sewage.
- the microorganisms in the activated sludge are used to remove the organic matter in the sewage, and at the same time, a part of the phosphorus and nitrogen are synergistically removed.
- the traditional activated sludge sewage biological treatment system is composed of an aeration tank (aerobic tank), a sedimentation tank, a sludge return system and an excess sludge removal system. Under artificial oxygenation conditions, various microbial populations in the treatment system are treated.
- activated sludge which utilizes microbial coagulation, adsorption and oxidation in the activated sludge to decompose and remove organic pollutants in the sewage.
- the sludge is then separated from the water, and most of the sludge is returned to the aeration tank to form a mixed liquid (activated sludge mixture), and the excess is discharged from the activated sludge system.
- Activated sludge sewage biological nitrogen removal technology is a biological biological nitrogen removal treatment method developed on the basis of traditional activated sludge method. Its biological nitrogen removal includes ammonia conversion, nitrification and denitrification. .
- the organic nitrogen in the wastewater is converted into ammonia nitrogen by the ammoniation reaction under the action of ammoniated bacteria. Together with the original ammonia nitrogen in the wastewater, it is oxidized to nitrate by nitrification under the action of nitrifying microorganisms under sufficient oxygen supply and other suitable conditions.
- Nitrogen nitrite and nitrate
- molecular nitrogen which is harmless to the human body, by denitrification under the action of denitrifying microorganisms under anaerobic conditions. Therefore, the various forms of nitrogen in the sewage are converted into nitrogen and discharged into the atmosphere through the above-mentioned reaction process, which is also the main purpose and way of biological nitrogen removal.
- the sewage biological nitrogen removal system is shown in Figure 1. It consists of primary sedimentation tank 1, anoxic tank 2, aerobic tank 3, secondary settling tank 4, mixed liquor internal circulation system 5, sludge return system 6 and so on.
- the sewage is first precipitated from the primary sedimentation tank 1, and the initially precipitated sludge is discharged from the bottom of the primary sedimentation tank 1.
- mechanical mixing is generally required to maintain the mixed state of the activated sludge mixture.
- aerobic tank 3 mechanical or blast aeration is generally used to ensure sufficient oxygen for the activated sludge microorganisms.
- the nitrate can be returned to the anoxic tank 2 via the mixed liquor internal circulation system 5, or the nitrate can be returned to the anoxic tank 2 via the sludge return system 6; denitrification in the anoxic tank 2
- the microorganism reduces the nitrate to nitrogen or gaseous nitrogen oxides to achieve biological nitrogen removal; in the aerobic tank 3, organic matter oxidation reaction and nitrogen nitrification reaction occur.
- various biological carriers or artificially cultured nitrifying microorganisms are required to be added to the aerobic tank 3 of the biological biological nitrogen removal system.
- the treated sewage is discharged from the upper part of the secondary settling tank 4, and the excess sludge is returned or discharged from the bottom of the secondary settling tank 4.
- the amination process is carried out by bacteria, fungi and actinomycetes which are widely found in nature and have the ability to decompose proteins and their nitrogen-containing derivatives. Usually, they are not restrictive to the biological nitrogen removal of sewage.
- the denitrification process is also carried out by heterotrophic denitrifying microorganisms, which are facultative bacteria that utilize N 5+ and N in nitrates and nitrites in the absence of oxygen and nitrates. 3+ acts as an electron acceptor in energy metabolism, and uses organic matter as a carbon source and an electron donor to reduce nitrate nitrogen to nitrogen.
- the denitrification process acts as a complex biochemical reaction process, it is affected by reaction temperature, pH, dissolved oxygen, inhibitory substances, and available carbon sources. In general, as long as the available carbon source is sufficient, the denitrification process will not become a restrictive process affecting the biological nitrogen removal of sewage.
- the nitrification process it is completed by two groups of autotrophic aerobic microorganisms through two processes: the first step is to convert ammonia nitrogen into nitrite by nitrite, and the second step is to nitric acid by nitric acid. The salt is converted to nitrate.
- nitrite bacteria and the nitric acid bacteria are generally referred to as nitrifying microorganisms (or nitrifying bacteria), which are obligate aerobic bacteria, using inorganic compounds such as CO-, HC0 3 - and C0 2 as carbon sources, from oxidizing NH or N0 2 - The process of obtaining energy to complete the metabolic reaction.
- Nitrifying bacteria have a small rate of growth and a low yield compared to heterogeneous microorganisms, making the proportion of nitrifying bacteria in activated sludge small (about 5%). Therefore, the nitrification process is greatly affected by factors such as alkalinity and pH, inhibitory substances, matrix (ammonia nitrogen and dissolved oxygen), organic load, and reaction temperature.
- the reaction temperature is generally an uncontrollable condition for a large-scale sewage treatment process, but for microorganisms involved in the nitrification reaction, the optimum growth temperature of the nitrite bacteria is 35 ° C, and the optimal growth temperature of the nitric acid bacteria is At 35 ⁇ 42 °C, the decrease of reaction temperature not only causes the decrease of the specific growth rate of nitrifying bacteria, but also causes the activity of nitrifying bacteria to be greatly reduced to a large extent. The decrease of nitrification activity directly leads to the decrease of nitrification ability and efficiency of the treatment system. Completely destroyed.
- the nitrification process is a restrictive process affecting the biological nitrogen removal capacity of sewage, and the effect of reaction temperature on the activity of nitrifying microorganisms, especially the nitrification under low temperature (less than 12 °C) has become a limiting bottleneck for biological nitrogen removal of sewage. problem.
- iron hydroxide acts as a water purifying agent, a catalyst, an absorbent, and an arsenic antidote in the water treatment process, and has the functions of adsorption and coagulation.
- the preparation of traditional ferric hydroxide requires the use of special equipment such as reactors, which not only has complicated equipment, low production efficiency, heat and loss of medicine in the production process, but also cannot achieve rapid use of ferric hydroxide after preparation, especially iron hydroxide.
- aging phenomenon is inevitable, and the iron hydroxide colloid condenses and precipitates, which affects the effect of the final use.
- there is a problem of chemical mixing control in the preparation process there is a problem of chemical mixing control in the preparation process.
- the iron hydroxide prepared by the preparation has a deeper color in the precipitation and heating process, and is harder to dissolve in the acid (or alkali), and the chemical activity is relatively weakened. This phenomenon is the aging phenomenon of the iron hydroxide, and the aging effect is finally The chemical activity of the iron hydroxide is lowered, and the action ability and efficiency of the iron hydroxide as a water purifying agent, a catalyst, an absorbent, and an arsenic antidote are adversely affected during the water treatment.
- the invention aims to solve the problem of the influence of low temperature conditions on the microbial function microbial activity, and provides a method for preparing ferric hydroxide in the field to increase the activity of nitrification function in the activated sludge, which prepares and adds ultrafine iron hydroxide to the activity in the field.
- the sludge system sewage biological nitrogen removal system
- the sludge system can increase the activity of nitrifying microorganisms, and can effectively solve the problem of poor running stability of existing biological biological nitrogen removal system and the influence of low temperature on nitrification function microbial activity, and increase nitrification function microorganisms.
- Biochemical reactivity improve the ability of biological nitrogen removal system to resist low temperature.
- the method for injecting iron hydroxide in the on-site preparation of the invention to increase the activity of nitrifying microbial activity in the activated sludge comprises the cultivation stage of the nitrifying microorganism and the long-term activity maintaining stage of the nitrifying microorganism, and the specific realization process is as follows -
- the concentration of 15% and 2.6% of ferric chloride solution (aqueous solution) and sodium bicarbonate solution (aqueous solution) are respectively set, and the concentration can effectively control the intensity of chemical reaction between ferric chloride and sodium bicarbonate.
- the conveying pipe allows the ferric chloride solution and the sodium bicarbonate solution to simultaneously enter the running centrifugal pump, and the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution to the centrifugal pump is a volume ratio of 1: 9, ferric chloride solution and carbonic acid.
- the flow rate of the sodium hydrogen solution is not less than 1.0 m / sec, and the ferric chloride solution and the sodium hydrogencarbonate solution are chemically reacted by stirring and mixing the centrifugal pump impeller in a centrifugal pump to form an ultrafine hydroxide having a mass concentration of 10%.
- the iron solution, the generated ultrafine iron hydroxide solution is continuously discharged from the outlet of the centrifugal pump;
- the ultrafine iron hydroxide solution continuously discharged from the outlet of the centrifugal pump is directly added to the activated sludge mixture in the aerobic tank of the biological nitrogen removal system, and the biological nitrogen removal system refers to the stable operation of the nitrifying microorganism.
- the nitrification function microorganism has a normal nitrification function of the sewage biological nitrogen removal system, and the dosage of the ultrafine iron hydroxide solution is controlled in the activated sludge mixture containing Fe amount of 5 mg/g ⁇ MLVSS ⁇ c!
- the addition point of the ultrafine iron hydroxide solution varies depending on the aerobic reaction type.
- the ultrafine iron hydroxide solution is directly added to the central part of the aerobic tank.
- the ultrafine iron hydroxide is directly added to the middle part of the aerobic tank corridor, that is, according to the theoretical hydraulic retention time.
- the activated sludge flows through the aerobic tank for a period of 1. 5 hours to 2. 5 hours in the corridor, and utilizes aeration mixing in the aerobic tank to achieve ultra-fine iron hydroxide and activated sludge.
- the total dosage of the ultrafine iron hydroxide is controlled to control the iron content in the activated sludge mixture to reach 30 ⁇ 50mgFe/g ⁇ MLVSS (mixed liquid volatile suspended solids concentration); keep the sewage biologically removed during the cultivation process
- the original influent load condition of the nitrogen system is unchanged, and the activated sludge sludge age is gradually extended to reach 1 to 2 times of the designed sludge age satisfying the normal nitrification load condition, and the time required for the cultivation process is 10 to 20 days.
- the above-mentioned nitrification function microbial culture process uses the centrifugal pump to prepare the ultrafine iron hydroxide into the aerobic tank, and the mixing of the medicament in the pump impeller of the centrifugal pump realizes rapid online real-time preparation and immediate use, avoiding storage after preparation of the iron hydroxide.
- the prepared iron hydroxide colloid is an aggregate of amorphous ultrafine primary particles (about 5 nm), has ultrafine particle high dispersibility and very high chemical activity, and Fe produced by the method (0H) 3 Colloid has the functions of super-adsorption and coagulation, and combines with the activated sludge flocs by electric neutralization, adsorption bridging and flocculation, to produce bioflocs with dense floc structure.
- the combination with the chemical flocs improves the flocculation performance of the activated sludge flocs and improves the separation effect of the activated sludge mixture.
- the specific dosage is calculated according to the amount of iron loss in the biological nitrogen removal system of the sewage caused by the excess sludge discharge.
- the salt chemical injection point is consistent with the culture stage; at this stage, the iron ion is intervened in the activated sludge microbial metabolic process with denitrification function, and the iron ion is involved in the electron transport and the enzymatic reaction activator, which can effectively improve the biochemical reaction metabolism of the microorganism. Active, and promotes bacterial growth and enzyme secretion, thereby forming nitrate with higher biological metabolic activity Functional activated sludge.
- the invention utilizes the combination of iron and activated sludge microorganisms through chemical and biochemical, strengthens the electron transfer action of iron element in the nitrifying bacterial cells and the action of the enzymatic activator, can effectively improve the biochemical reaction metabolic activity of the nitrifying microorganism, and promote The proliferation of nitrifying microbes and the secretion of enzymes in microbial cells, while avoiding the toxic effects of excessive iron on microorganisms, thus forming a nitrification functional activated sludge with high bio-metabolism activity.
- the invention solves the cultivation problem of the microorganism with high activity nitrification function and the stable operation problem of the microorganism with high activity nitrification function, realizes the rapid combination of the iron element and the activated sludge, and utilizes the electron transfer of the iron element in the nitrification function microbial cell.
- the action acts as an activator of the enzymatic reaction to maintain high activity of the nitrifying functional microorganism for a long period of time.
- the invention improves the applicability of the biological nitrogen removal technology of sewage, solves the bottleneck problem of the biological nitrogen removal system of the sewage, and the system has the obvious enhancement of the low temperature resistance, and the nitrification efficiency can be maintained above 70% under the condition that the reaction temperature is lower than 1CTC.
- the denitrification efficiency is over 85%. Since only a small amount of Fe ions are directly administered during the aerobic reaction of the biological nitrogen and phosphorus removal system, instead of adding various biological carriers or artificially cultured nitrifying microorganisms to solve the nitrification problem, not only the dosing method is simple and reliable, but also management.
- Figure 1 is a schematic view showing the structure of a sewage biological nitrogen removal system.
- the invention directly feeds fresh un-aged iron hydroxide prepared on site into an aerobic tank in a sewage biological nitrogen removal system, and strengthens iron by combining iron hydroxide flocs with activated sludge microbial flocs. Ions participate in the interaction of electron transport and enzymatic activator, which not only effectively enhances the biochemical reaction metabolic activity of microorganisms, but also improves and strengthens the floc structure of activated sludge, forming nitrification with high reactivity and floc stability. Functional activated sludge, the final activated sludge mixture is separated into muddy water in the secondary settling tank, and the activated sludge supernatant is separated for further treatment or discharge.
- the sewage biological nitrogen removal system refers to the nitrification function microorganisms in the stable operation state or the nitrification function microorganisms have the normal nitrification function of the sewage biological nitrogen removal system
- the process for preparing an ultrafine iron hydroxide solution having a concentration of 10% as a raw material is as follows:
- the concentration of ferric chloride solution and the concentration of sodium bicarbonate solution should be controlled within 15% and 2.6%, respectively.
- a ferric chloride solution (aqueous solution) and a sodium hydrogencarbonate solution (aqueous solution) having a mass concentration of 15% and 2.6% were respectively disposed, and the ferric chloride solution and the sodium hydrogencarbonate solution were simultaneously put into operation through a conveying pipe.
- the centrifugal pump 7 see Fig.
- the ferric chloride solution or the sodium hydrogencarbonate solution can be accurately conveyed by the metering pump, and the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution to the centrifugal pump 7 is a volume ratio of 1: 9, the liquid flow rate is not less than 1. 0 m / sec.
- the pipe diameter of the ferric chloride solution and the sodium bicarbonate solution can be determined by combining the parameters of the metering pump, the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution, and the flow rate.
- the ferric chloride solution and the sodium bicarbonate solution are chemically reacted by agitation mixing of the centrifugal pump impeller in a centrifugal pump to form an ultrafine iron hydroxide solution having a mass concentration of 10%, and the resulting ultrafine iron hydroxide solution is formed by a centrifugal pump.
- the exit of 7 is continuously discharged.
- Ferric hydroxide has amphoteric properties, but its basicity is stronger than acidity.
- the newly prepared iron hydroxide is easily soluble in inorganic acids and organic acids, and is also soluble in hot concentrated alkali.
- the ferric hydroxide is easily changed in nature after being placed or heated (even for a short period of time). The solubility in the acid is now reduced, especially as the residence time increases, the more difficult it is to dissolve in the acid.
- the present invention adopts an on-site preparation method to avoid the problem of a decrease in reaction efficiency caused by storage aging after the preparation of iron hydroxide.
- the new ecological Fe (0H) 3 colloid has the functions of super-adsorption and coagulation, and combines with the activated sludge flocs through the electric neutralization, adsorption bridging and flocculation of the flocs to form a dense floc structure.
- a combination of biological flocs and chemical flocs having a specific gravity slightly larger than 1.0. Thereby, the flocculation performance of the activated sludge flocs is improved, and the separation effect of the activated sludge mixture is improved.
- the iron hydroxide solution prepared by the above method is used for culturing the nitrifying function microorganisms, and the specific process is as follows:
- the nitrification function microorganisms in the system are in a stable operation state, or the continuous nitrification function is ensured by continuous culture.
- the microorganism has a normal nitrification function, and on the basis of this, a highly active nitrifying microorganism is cultured.
- the ultrafine iron hydroxide is directly added to the central part of the aerobic tank of the biological denitrification system;
- the push-flow aerobic tank the ultra-fine iron hydroxide directly is added to the middle and front sections of the aerobic pool corridor of the biological nitrogen removal system, that is, the time period of the activated sludge flowing through the aerobic tank according to the theoretical hydraulic retention time is 1 In the corridor between 5h and 2.
- the aerobic mixing in the aerobic tank is used to achieve rapid mixing of the ultrafine iron hydroxide with the activated sludge.
- the total dosage of the ultrafine iron hydroxide (Fe (0H) 3 concentration of 10%) is controlled to be 30 ⁇ 50mgFe/g in the activated sludge mixture.
- the method of the present invention comprises a culture stage of a nitrifying functional microorganism and a long-term activity maintaining stage of the nitrifying functional microorganism, and the long-term activity maintaining phase of the nitrifying functional microorganism is maintained after the end of the nitrifying functional microbial culture stage.
- iron salt chemicals FeCl 2 , FeS0 4 or FeCl 3
- the iron salt chemical dosage point is consistent with the cultivation stage.
- the amount of iron in the iron salt chemical added per liter of sewage treated in the sewage biological nitrogen removal system is lag - 2mg, the investment
- the addition amount is only used as a supplement to the iron element lost from the excess sludge discharge.
- the specific dosage is calculated according to the amount of iron loss in the biological biological nitrogen removal system caused by the excess sludge discharge.
- iron ions are involved in the metabolic process of activated sludge microorganisms with denitrification function, and strengthen the role of iron ions in electron transfer and enzymatic reaction activators, which can effectively increase the biochemical reaction metabolic activity of microorganisms, and also promote bacterial reproduction and enzyme secretion. It has a promoting effect, thereby forming a nitrifying functional activated sludge with high bio-metabolism activity.
- iron ions are intervened in the activated sludge microbial metabolic process with denitrification function under artificial control, and iron ions are involved in electron transfer and enzymatic promotion.
- the action activator not only effectively increases the biochemical reaction metabolic activity of the microorganism, but also improves and strengthens the floc structure of the activated sludge, forming a new activated sludge with high reactivity and floc stability;
- Iron salt is a good coagulant.
- the pH value (alkalinity) of the system changes, the iron hydroxide is further hydrolyzed and complexed to form complex cations or complex anions with different charges.
- the bridging action of hydroxyl group (0H) in the polynuclear hydroxy complex can produce an inorganic polymer material having a polymerization degree of 2 to 900, which not only can enhance the adsorption of activated sludge, but also can be combined with various metals.
- the hydroxide reacts co-precipitation, removes heavy metals that have an inhibitory effect on certain enzymes, and acts as a shielding organism.
- the action of the reaction enzyme inhibitor further enhances the biochemical reactivity of the activated sludge.
- the main process design parameters of the biological nitrogen removal system after iron hydroxide strengthening are as follows:
- the system processing load is significantly improved, and the volumetric loading rate is doubled compared to the traditional biological nitrogen removal system.
- the amount of excess sludge is small (reduced by 20 ⁇ 30%), which reduces the sludge treatment load and cost.
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Abstract
Provided is a process for increasing the activity of a nitrification microorganism in an active sludge by in-situ preparation and addition of iron hydroxide, comprising a culturing stage for a nitrification microorganism and a long-term activity-maintaining stage, wherein the culturing stage is for increasing the activity of the nitrification microorganism by in-situ preparation and addition of ultra fine particles of iron hydroxide at a mass concentration of 10% in an active sludge system facility, the in-situ preparation being achieved by chemically reacting iron trichloride solution at a mass concentration of 15% and with a 2.6% sodium hydrogen carbonate solution under mixing and stirring in a centrifugal pump, and the long-term activity-maintaining stage involving adding a chemical reagent of an iron salt directly to the active sludge mixture solution, in order to supplement the iron element lost by discharging the remaining sludge. The process improves low temperature resistance of a biological denitrogenation system.
Description
现场制备投加氢氧化铁提高活性污泥内硝化功能微生物活性的方法 技术领域 Method for preparing ferric hydroxide in situ to increase nitrification function microbial activity in activated sludge
本发明涉及一种提高用于污水生物脱氮处理的活性污泥内硝化微生物在低温条件下的硝 化能力的方法， 属于污水处理技术领域。 The invention relates to a method for improving the nitrification ability of nitrifying microorganisms in activated sludge for biological denitrification treatment of sewage under low temperature conditions, and belongs to the technical field of sewage treatment.
背景技术 Background technique
活性污泥法是一种污水的生物处理方法， 是通过活性污泥内的微生物去除污水中的有机 物， 同时协同去除一部分磷素和氮素。 传统的活性污泥污水生物处理***是由曝气池 （好氧 池）、 沉淀池、 污泥回流***和剩余污泥排除***组成， 在人工充氧条件下， 对处理***内 各种微生物群体进行连续混合培养， 形成活性污泥， 利用活性污泥中的微生物凝聚、 吸 附和氧化作用， 以分解去除污水中的有机污染物。 然后使污泥与水分离， 大部分污泥再 回流到曝气池形成混合液 （活性污泥混合液）， 多余部分则排出活性污泥***。 The activated sludge process is a biological treatment method for sewage. The microorganisms in the activated sludge are used to remove the organic matter in the sewage, and at the same time, a part of the phosphorus and nitrogen are synergistically removed. The traditional activated sludge sewage biological treatment system is composed of an aeration tank (aerobic tank), a sedimentation tank, a sludge return system and an excess sludge removal system. Under artificial oxygenation conditions, various microbial populations in the treatment system are treated. Continuous mixed culture is carried out to form activated sludge, which utilizes microbial coagulation, adsorption and oxidation in the activated sludge to decompose and remove organic pollutants in the sewage. The sludge is then separated from the water, and most of the sludge is returned to the aeration tank to form a mixed liquid (activated sludge mixture), and the excess is discharged from the activated sludge system.
活性污泥污水生物脱氮技术是在传统活性污泥法基础上发展而来的一种污水生物脱氮处 理方法， 其生物脱氮包括氨化作用、 硝化作用和反硝化作用等氮的转化过程。 废水中的有机 氮在氨化细菌的作用下通过氨化反应转化为氨氮， 与废水中原有的氨氮一起， 在供氧充足及 其它合适条件下， 在硝化微生物作用下通过硝化反应被氧化成硝态氮 （亚硝酸盐和硝酸盐）， 硝态氮在无氧条件下可在反硝化微生物作用下通过反硝化反应转化为对人体无害的分子态氮 气。 因此， 通过上述反应过程将污水中各种形态的氮转化为氮气并排入大气中， 也是目前生 物脱氮的主要目的和途径。 Activated sludge sewage biological nitrogen removal technology is a biological biological nitrogen removal treatment method developed on the basis of traditional activated sludge method. Its biological nitrogen removal includes ammonia conversion, nitrification and denitrification. . The organic nitrogen in the wastewater is converted into ammonia nitrogen by the ammoniation reaction under the action of ammoniated bacteria. Together with the original ammonia nitrogen in the wastewater, it is oxidized to nitrate by nitrification under the action of nitrifying microorganisms under sufficient oxygen supply and other suitable conditions. Nitrogen (nitrite and nitrate), nitrate-nitrogen can be converted to molecular nitrogen, which is harmless to the human body, by denitrification under the action of denitrifying microorganisms under anaerobic conditions. Therefore, the various forms of nitrogen in the sewage are converted into nitrogen and discharged into the atmosphere through the above-mentioned reaction process, which is also the main purpose and way of biological nitrogen removal.
污水生物脱氮***如图 1所示， 由初沉池 1、 缺氧池 2、 好氧池 3、 二沉池 4、 混合液内 循环*** 5、 污泥回流*** 6等组成。 污水先由初沉池 1沉淀， 初步沉淀的污泥由初沉池 1 的底部排放。 缺氧池 2内一般需要采用机械搅拌方式保持活性污泥混合液的混合状态， 好氧 池 3内一般采用机械或鼓风曝气方式保证为活性污泥微生物提供足够的氧。 根据工艺运行方 式变化， 可以通过混合液内循环*** 5将硝酸盐回流到缺氧池 2， 也可以通过污泥回流*** 6 将硝酸盐回流到缺氧池 2 ; 缺氧池 2 内通过反硝化微生物将硝酸盐还原为氮气或气态氮氧化 物实现生物脱氮； 好氧池 3内发生有机物氧化反应与氮的硝化反应。 通常为了解决硝化问题 需要通过向污水生物脱氮***好氧池 3内投加各种生物载体或人工培养的硝化微生物。 处理 后的污水由二沉池 4上部排出， 多余污泥由二沉池 4底部回流或排出。 The sewage biological nitrogen removal system is shown in Figure 1. It consists of primary sedimentation tank 1, anoxic tank 2, aerobic tank 3, secondary settling tank 4, mixed liquor internal circulation system 5, sludge return system 6 and so on. The sewage is first precipitated from the primary sedimentation tank 1, and the initially precipitated sludge is discharged from the bottom of the primary sedimentation tank 1. In the anoxic tank 2, mechanical mixing is generally required to maintain the mixed state of the activated sludge mixture. In the aerobic tank 3, mechanical or blast aeration is generally used to ensure sufficient oxygen for the activated sludge microorganisms. Depending on the mode of operation of the process, the nitrate can be returned to the anoxic tank 2 via the mixed liquor internal circulation system 5, or the nitrate can be returned to the anoxic tank 2 via the sludge return system 6; denitrification in the anoxic tank 2 The microorganism reduces the nitrate to nitrogen or gaseous nitrogen oxides to achieve biological nitrogen removal; in the aerobic tank 3, organic matter oxidation reaction and nitrogen nitrification reaction occur. Usually, in order to solve the problem of nitrification, various biological carriers or artificially cultured nitrifying microorganisms are required to be added to the aerobic tank 3 of the biological biological nitrogen removal system. The treated sewage is discharged from the upper part of the secondary settling tank 4, and the excess sludge is returned or discharged from the bottom of the secondary settling tank 4.
在上述反应过程中， 氨化过程是由自然界广泛存在的具有分解蛋白质及其含氮衍生物能 力的细菌、 真菌和放线菌来完成的， 通常其不会成为影响污水生物脱氮的限制性过程； 反硝 化过程亦由异养性反硝化微生物完成的， 反硝化微生物属兼性菌， 其在无氧而有硝酸盐存在 的条件下， 利用硝酸盐和亚硝酸盐中的 N5+和 N3+作为能量代谢中的电子受体， 以有机物作为碳 源和电子供体将硝态氮还原为氮气。 虽然反硝化过程作为一复杂的生物化学反应过程， 其受 反应温度、 pH值、 溶解氧、 抑制物质以及可利用碳源的影响。 一般来说， 只要可利用碳源充 足， 反硝化过程也不会成为影响污水生物脱氮的限制性过程。 然而对于硝化过程而言， 其由 两组化能自养型好氧微生物通过两个过程来完成的， 第一步由亚硝酸菌将氨氮转化为亚硝酸 盐，第二步硝酸菌将亚硝酸盐转化为硝酸盐。通常将亚硝酸菌与硝酸菌统称为硝化微生物（或 硝化细菌）， 其属专性好氧菌， 利用无机化合物如 CO —、 HC03—和 C02作碳源， 从氧化 NH 或 N02—
的过程中获得能量完成新陈代谢反应。 由于与异样微生物相比， 硝化细菌的比增长速率小， 产率低， 使硝化细菌在活性污泥中所占的比例很小 （约为 5%)。 因此， 硝化过程受碱度与 pH 值、 抑制物质、 基质（氨氮与溶解氧）、 有机负荷、 反应温度等因素影响较大。 在上述影响因 素中， 反应温度一般为大规模污水处理过程的不可控条件， 但对于参与硝化反应的微生物而 言， 亚硝酸菌最佳生长温度为 35°C， 硝酸菌的最佳生长温度为 35〜42°C， 反应温度的降低不 但导致硝化细菌的比增长速率的下降， 同时更大程度上导致硝化细菌活性的大幅度降低， 硝 化活性的降低直接导致处理***硝化能力与效率的下降甚至完全破坏。 因此， 硝化过程是影 响污水生物脱氮能力的限制性过程， 而反应温度对硝化微生物活性的影响， 特别是低温 （小 于 12°C ) 条件下的硝化问题已成为污水生物脱氮的限制性瓶颈问题。 In the above reaction process, the amination process is carried out by bacteria, fungi and actinomycetes which are widely found in nature and have the ability to decompose proteins and their nitrogen-containing derivatives. Usually, they are not restrictive to the biological nitrogen removal of sewage. The denitrification process is also carried out by heterotrophic denitrifying microorganisms, which are facultative bacteria that utilize N 5+ and N in nitrates and nitrites in the absence of oxygen and nitrates. 3+ acts as an electron acceptor in energy metabolism, and uses organic matter as a carbon source and an electron donor to reduce nitrate nitrogen to nitrogen. Although the denitrification process acts as a complex biochemical reaction process, it is affected by reaction temperature, pH, dissolved oxygen, inhibitory substances, and available carbon sources. In general, as long as the available carbon source is sufficient, the denitrification process will not become a restrictive process affecting the biological nitrogen removal of sewage. However, for the nitrification process, it is completed by two groups of autotrophic aerobic microorganisms through two processes: the first step is to convert ammonia nitrogen into nitrite by nitrite, and the second step is to nitric acid by nitric acid. The salt is converted to nitrate. The nitrite bacteria and the nitric acid bacteria are generally referred to as nitrifying microorganisms (or nitrifying bacteria), which are obligate aerobic bacteria, using inorganic compounds such as CO-, HC0 3 - and C0 2 as carbon sources, from oxidizing NH or N0 2 - The process of obtaining energy to complete the metabolic reaction. Nitrifying bacteria have a small rate of growth and a low yield compared to heterogeneous microorganisms, making the proportion of nitrifying bacteria in activated sludge small (about 5%). Therefore, the nitrification process is greatly affected by factors such as alkalinity and pH, inhibitory substances, matrix (ammonia nitrogen and dissolved oxygen), organic load, and reaction temperature. Among the above influencing factors, the reaction temperature is generally an uncontrollable condition for a large-scale sewage treatment process, but for microorganisms involved in the nitrification reaction, the optimum growth temperature of the nitrite bacteria is 35 ° C, and the optimal growth temperature of the nitric acid bacteria is At 35~42 °C, the decrease of reaction temperature not only causes the decrease of the specific growth rate of nitrifying bacteria, but also causes the activity of nitrifying bacteria to be greatly reduced to a large extent. The decrease of nitrification activity directly leads to the decrease of nitrification ability and efficiency of the treatment system. Completely destroyed. Therefore, the nitrification process is a restrictive process affecting the biological nitrogen removal capacity of sewage, and the effect of reaction temperature on the activity of nitrifying microorganisms, especially the nitrification under low temperature (less than 12 °C) has become a limiting bottleneck for biological nitrogen removal of sewage. problem.
因此， 对污水生物脱氮技术而言， 不仅存在脱氮运行稳定性问题， 而且低温对硝化微生 物活性影响问题目前尚无较好的解决办法，其也成为制约污水生物脱氮技术发展的瓶颈问题。 Therefore, for the biological nitrogen removal technology of sewage, there is not only the stability problem of denitrification operation, but also there is no good solution to the problem of the influence of low temperature on the activity of nitrifying microorganisms. It has also become a bottleneck restricting the development of biological nitrogen removal technology for sewage. .
众所周知， 氢氧化铁在水处理过程中作为净水剂、 催化剂、 吸收剂和砷解毒剂， 其具有 吸附及聚凝的功能。但是传统氢氧化铁制备均需利用反应釜等专用设备， 不仅存在设备复杂、 生产效率低与生产过程的热量、药品的损失问题， 而且无法实现制备后氢氧化铁的快速使用， 尤其氢氧化铁在转运、 存储过程中不可避免地出现陈化现象， 氢氧化铁胶体凝结沉淀， 影响 最终使用的效果， 同时还存在制备过程化学药剂混合控制问题。 制备获得的氢氧化铁在放置 沉淀和受热过程中沉淀颜色加深， 较难溶解于酸 (或碱）， 化学活泼性相对减弱， 该现象也就 是氢氧化铁的陈化现象， 该陈化作用最终导致氢氧化铁的化学活泼性下降， 对氢氧化铁在水 处理过程中作为净水剂、 催化剂、 吸收剂和砷解毒剂等作用能力与效率产生不利影响。 It is well known that iron hydroxide acts as a water purifying agent, a catalyst, an absorbent, and an arsenic antidote in the water treatment process, and has the functions of adsorption and coagulation. However, the preparation of traditional ferric hydroxide requires the use of special equipment such as reactors, which not only has complicated equipment, low production efficiency, heat and loss of medicine in the production process, but also cannot achieve rapid use of ferric hydroxide after preparation, especially iron hydroxide. In the process of transportation and storage, aging phenomenon is inevitable, and the iron hydroxide colloid condenses and precipitates, which affects the effect of the final use. At the same time, there is a problem of chemical mixing control in the preparation process. The iron hydroxide prepared by the preparation has a deeper color in the precipitation and heating process, and is harder to dissolve in the acid (or alkali), and the chemical activity is relatively weakened. This phenomenon is the aging phenomenon of the iron hydroxide, and the aging effect is finally The chemical activity of the iron hydroxide is lowered, and the action ability and efficiency of the iron hydroxide as a water purifying agent, a catalyst, an absorbent, and an arsenic antidote are adversely affected during the water treatment.
发明内容 Summary of the invention
本发明针对低温条件对硝化功能微生物活性影响问题， 提供一种现场制备投加氢氧化铁 提高活性污泥内硝化功能微生物活性的方法， 该方法通过现场制备并投加超微粒氢氧化铁至 活性污泥*** （污水生物脱氮***） 内来提高硝化功能微生物的活性， 能够有效解决现有污 水生物脱氮***存在的运行稳定性较差以及低温对硝化功能微生物活性影响问题， 提高硝化 功能微生物生化反应活性， 提高生物脱氮***抗低温影响能力。 The invention aims to solve the problem of the influence of low temperature conditions on the microbial function microbial activity, and provides a method for preparing ferric hydroxide in the field to increase the activity of nitrification function in the activated sludge, which prepares and adds ultrafine iron hydroxide to the activity in the field. The sludge system (sewage biological nitrogen removal system) can increase the activity of nitrifying microorganisms, and can effectively solve the problem of poor running stability of existing biological biological nitrogen removal system and the influence of low temperature on nitrification function microbial activity, and increase nitrification function microorganisms. Biochemical reactivity, improve the ability of biological nitrogen removal system to resist low temperature.
本发明的现场制备投加氢氧化铁提高活性污泥内硝化功能微生物活性的方法， 包括硝化 功能微生物的培养阶段和硝化功能微生物的长期运行活性保持阶段， 具体实现过程如下- The method for injecting iron hydroxide in the on-site preparation of the invention to increase the activity of nitrifying microbial activity in the activated sludge comprises the cultivation stage of the nitrifying microorganism and the long-term activity maintaining stage of the nitrifying microorganism, and the specific realization process is as follows -
( 1 ) 硝化功能微生物培养阶段- 首先以三氯化铁（FeCl3)和碳酸氢钠（NaHC03)为原料按以下方法在现场制备浓度为 10% 的超微粒氢氧化铁： (1) Nitrification function Microbial culture stage - First, the ultrafine iron hydroxide with a concentration of 10% was prepared on site by using ferric chloride (FeCl 3 ) and sodium bicarbonate (NaHC0 3 ) as follows:
分别配置质量浓度为 15%与 2. 6%的三氯化铁溶液（水溶液）和碳酸氢钠溶液（水溶液） ， 这样的浓度能够有效控制三氯化铁与碳酸氢钠化学反应的强度， 通过输送管道使三氯化铁溶 液和碳酸氢钠溶液同时进入运转的离心泵中， 三氯化铁溶液和碳酸氢钠溶液进入离心泵的比 例为体积比 1 : 9， 三氯化铁溶液和碳酸氢钠溶液的流速不小于 1. 0米 /秒， 三氯化铁溶液和碳 酸氢钠溶液在离心泵内通过离心泵叶轮的搅拌混合产生化学反应， 生成质量浓度为 10%的超 微粒氢氧化铁溶液， 生成的超微粒氢氧化铁溶液由离心泵的出口连续排出； The concentration of 15% and 2.6% of ferric chloride solution (aqueous solution) and sodium bicarbonate solution (aqueous solution) are respectively set, and the concentration can effectively control the intensity of chemical reaction between ferric chloride and sodium bicarbonate. The conveying pipe allows the ferric chloride solution and the sodium bicarbonate solution to simultaneously enter the running centrifugal pump, and the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution to the centrifugal pump is a volume ratio of 1: 9, ferric chloride solution and carbonic acid. The flow rate of the sodium hydrogen solution is not less than 1.0 m / sec, and the ferric chloride solution and the sodium hydrogencarbonate solution are chemically reacted by stirring and mixing the centrifugal pump impeller in a centrifugal pump to form an ultrafine hydroxide having a mass concentration of 10%. The iron solution, the generated ultrafine iron hydroxide solution is continuously discharged from the outlet of the centrifugal pump;
然后将由离心泵的出口连续排出的超微粒氢氧化铁溶液直接投加到生物脱氮***好氧池 内的活性污泥混合液中， 所述污水生物脱氮***是指硝化功能微生物已经处于稳定运行状态
或硝化功能微生物具有正常硝化功能的污水生物脱氮***， 超微粒氢氧化铁溶液投加量控制 在活性污泥混合液含 Fe量为 5mg/g · MLVSS · c！〜 10mg/g · MLVSS · d (在单位时间内向单位活 性污泥中投加 Fe的量）， 超微粒氢氧化铁溶液投加点根据好氧池反应型式而异， 对于完全混 合式好氧池， 超微粒氢氧化铁溶液直接投加在好氧池的中央部位， 对于推流式好氧池， 超微 粒氢氧化铁直接投加在好氧池廊道的中前段， 即按照理论水力停留时间计的活性污泥流经好 氧池的时间段为 1. 5小时〜 2. 5小时之间的廊道内， 并利用好氧池内的曝气混合作用实现超 微粒氢氧化铁与活性污泥的快速混合； 最终超微粒氢氧化铁的总投加量控制在活性污泥混合 液中含铁量达到 30〜50mgFe/g · MLVSS (混合液挥发性悬浮固体浓度） ； 在培养过程中保持 污水生物脱氮***原有进水负荷条件不变， 逐渐延长活性污泥泥龄， 使达到满足正常硝化负 荷条件的设计泥龄的 1〜2倍， 该培养过程所需时间为 10〜20天。 Then, the ultrafine iron hydroxide solution continuously discharged from the outlet of the centrifugal pump is directly added to the activated sludge mixture in the aerobic tank of the biological nitrogen removal system, and the biological nitrogen removal system refers to the stable operation of the nitrifying microorganism. State Or the nitrification function microorganism has a normal nitrification function of the sewage biological nitrogen removal system, and the dosage of the ultrafine iron hydroxide solution is controlled in the activated sludge mixture containing Fe amount of 5 mg/g · MLVSS · c! ~ 10mg/g · MLVSS · d (the amount of Fe added to the unit activated sludge per unit time), the addition point of the ultrafine iron hydroxide solution varies depending on the aerobic reaction type. For a fully mixed aerobic tank, The ultrafine iron hydroxide solution is directly added to the central part of the aerobic tank. For the push-flow aerobic tank, the ultrafine iron hydroxide is directly added to the middle part of the aerobic tank corridor, that is, according to the theoretical hydraulic retention time. The activated sludge flows through the aerobic tank for a period of 1. 5 hours to 2. 5 hours in the corridor, and utilizes aeration mixing in the aerobic tank to achieve ultra-fine iron hydroxide and activated sludge. Mixing; The total dosage of the ultrafine iron hydroxide is controlled to control the iron content in the activated sludge mixture to reach 30~50mgFe/g · MLVSS (mixed liquid volatile suspended solids concentration); keep the sewage biologically removed during the cultivation process The original influent load condition of the nitrogen system is unchanged, and the activated sludge sludge age is gradually extended to reach 1 to 2 times of the designed sludge age satisfying the normal nitrification load condition, and the time required for the cultivation process is 10 to 20 days.
上述硝化功能微生物培养过程利用离心泵现场制备获得超微粒氢氧化铁投入到好氧池 内， 药剂在离心泵泵腔叶轮内的混合实现了快速在线实时制备与即时使用， 避免氢氧化铁制 备后存储陈化导致的反应效率下降问题， 制备的氢氧化铁胶体为无定形超微粒一次粒子 （约 5nm)的集合体， 具有超微粒高分散性和非常高的化学活泼性， 利用该方法生成的 Fe (0H) 3胶 体具有超强吸附及聚凝的功能， 并通过电中和、 吸附架桥及絮体的卷扫作用与活性污泥絮体 进行结合， 生成具有絮体结构密实的生物絮体与化学絮体的结合体， 由此提高了活性污泥絮 体的絮凝性能， 改善了活性污泥混合液的分离效果。 The above-mentioned nitrification function microbial culture process uses the centrifugal pump to prepare the ultrafine iron hydroxide into the aerobic tank, and the mixing of the medicament in the pump impeller of the centrifugal pump realizes rapid online real-time preparation and immediate use, avoiding storage after preparation of the iron hydroxide. The problem of the decrease in reaction efficiency caused by aging, the prepared iron hydroxide colloid is an aggregate of amorphous ultrafine primary particles (about 5 nm), has ultrafine particle high dispersibility and very high chemical activity, and Fe produced by the method (0H) 3 Colloid has the functions of super-adsorption and coagulation, and combines with the activated sludge flocs by electric neutralization, adsorption bridging and flocculation, to produce bioflocs with dense floc structure. The combination with the chemical flocs improves the flocculation performance of the activated sludge flocs and improves the separation effect of the activated sludge mixture.
(2)硝化功能微生物培养阶段结束后进入硝化功能微生物的长期运行活性保持阶段， 随 着微生物絮体与氢氧化铁絮体结合体的形成与稳定， 向生物脱氮***好氧池内的活性污泥混 合液中直接投加铁盐化学药剂 （FeCl2、 FeSO, 或 FeCl3), 以补充铁元素的流失量， 污水生物 脱氮***中每处理一升污水补充投加的铁盐化学药剂中铁元素的量为 lmg - 2mg， 该投加量仅 作为随剩余污泥排放流失铁元素的补充， 具体投加量按照剩余污泥排放导致的污水生物脱氮 ***内铁元素的流失量计算， 铁盐化学药剂投加点与培养阶段一致； 此阶段铁离子介入具有 脱氮功能的活性污泥微生物代谢过程，强化铁离子参与电子传递作用与酶促反应激活剂作用， 能够有效提高微生物的生化反应代谢活性， 而且对细菌繁殖和酶的分泌有着促进作用， 由此 形成具有较高生物代谢活性的硝化功能活性污泥。 (2) Nitrification function After the end of the microbial culture stage, the long-term activity retention stage of the nitrifying function microorganisms is maintained. With the formation and stabilization of the combination of microbial flocs and ferric hydroxide floes, the active decontamination into the aerobic tank of the biological nitrogen removal system The iron salt chemical agent (FeCl 2 , FeSO, or FeCl 3 ) is directly added to the mud mixture to supplement the loss of iron. In the sewage biological nitrogen removal system, one liter of sewage is treated for each additional iron salt chemical agent. The amount of the element is 1mg - 2mg, and the dosage is only used as a supplement to the iron element lost with the excess sludge discharge. The specific dosage is calculated according to the amount of iron loss in the biological nitrogen removal system of the sewage caused by the excess sludge discharge. The salt chemical injection point is consistent with the culture stage; at this stage, the iron ion is intervened in the activated sludge microbial metabolic process with denitrification function, and the iron ion is involved in the electron transport and the enzymatic reaction activator, which can effectively improve the biochemical reaction metabolism of the microorganism. Active, and promotes bacterial growth and enzyme secretion, thereby forming nitrate with higher biological metabolic activity Functional activated sludge.
本发明利用铁元素与活性污泥微生物通过化学与生物化学的结合作用， 强化铁元素在硝 化细菌细胞内的电子传递作用与酶促激化剂作用， 能够有效提高硝化微生物的生化反应代谢 活性， 促进硝化功能微生物的繁殖与微生物细胞内酶的分泌， 同时避免过量铁元素对微生物 的毒害影响， 由此形成了具有较高生物代谢活性的硝化功能活性污泥。 本发明解决了具有高 活性硝化功能微生物的培养问题和具有高活性硝化功能微生物的稳定运行问题， 实现了铁元 素与活性污泥的快速结合， 并利用铁元素在硝化功能微生物细胞内的电子传递作用与酶促反 应的激化剂作用， 使硝化功能微生物长期保持高活性。 The invention utilizes the combination of iron and activated sludge microorganisms through chemical and biochemical, strengthens the electron transfer action of iron element in the nitrifying bacterial cells and the action of the enzymatic activator, can effectively improve the biochemical reaction metabolic activity of the nitrifying microorganism, and promote The proliferation of nitrifying microbes and the secretion of enzymes in microbial cells, while avoiding the toxic effects of excessive iron on microorganisms, thus forming a nitrification functional activated sludge with high bio-metabolism activity. The invention solves the cultivation problem of the microorganism with high activity nitrification function and the stable operation problem of the microorganism with high activity nitrification function, realizes the rapid combination of the iron element and the activated sludge, and utilizes the electron transfer of the iron element in the nitrification function microbial cell. The action acts as an activator of the enzymatic reaction to maintain high activity of the nitrifying functional microorganism for a long period of time.
本发明提高了污水生物脱氮技术的适用性， 解决了污水生物脱氮***存在的瓶颈问题， ***抗低温能力得到明显增强， 在反应温度低于 1CTC条件下， 硝化效率可以保持 70%以上， 脱氮效率达到 85%以上。 由于仅采用在生物脱氮除磷***好氧反应过程中直接投药少量的 Fe 离子， 取代了为解决硝化问题而投加各种生物载体或人工培养的硝化微生物， 不仅加药方式 简单可靠， 管理方便， 而且投资与运行成本低， 特别适于城镇污水与具有类似水质条件的工
业废水的脱氮处理以及有毒有害、 难降解工业废水的生物处理的应用。 适合于新建污水脱氮 ***硝化功能的强化与现有实际生产***的升级改造， 对解决污水生物脱氮运行稳定性与低 温硝化瓶颈问题具有实际意义。 The invention improves the applicability of the biological nitrogen removal technology of sewage, solves the bottleneck problem of the biological nitrogen removal system of the sewage, and the system has the obvious enhancement of the low temperature resistance, and the nitrification efficiency can be maintained above 70% under the condition that the reaction temperature is lower than 1CTC. The denitrification efficiency is over 85%. Since only a small amount of Fe ions are directly administered during the aerobic reaction of the biological nitrogen and phosphorus removal system, instead of adding various biological carriers or artificially cultured nitrifying microorganisms to solve the nitrification problem, not only the dosing method is simple and reliable, but also management. Convenient, and low investment and operating costs, especially suitable for urban sewage and workers with similar water quality conditions Denitrification treatment of industrial wastewater and application of biological treatment of toxic and harmful and difficult to degrade industrial wastewater. It is suitable for the strengthening of nitrification function of new sewage denitrification system and the upgrading of existing actual production system, which has practical significance for solving the problem of stable biological nitrogen denitrification operation and bottleneck of low temperature nitrification.
附图说明 DRAWINGS
图 1是污水生物脱氮***的结构示意图。 Figure 1 is a schematic view showing the structure of a sewage biological nitrogen removal system.
其中： 1、 初沉池， 2、 缺氧池， 3、 好氧池， 4、 二沉池， 5、 混合液内循环***， 6、 污 泥回流***， 7、 离心泵。 Among them: 1, primary sedimentation tank, 2, anoxic pool, 3, aerobic tank, 4, secondary settling tank, 5, mixed liquid internal circulation system, 6, sewage return system, 7, centrifugal pump.
具体实施方式 detailed description
本发明是将现场制备的新鲜的未经陈化的氢氧化铁直接投加到污水生物脱氮***中的好 氧池内， 通过氢氧化铁絮体与活性污泥微生物絮体的结合， 强化铁离子参与电子传递作用与 酶促反应激活剂作用， 不仅有效提高微生物的生化反应代谢活性， 而且改进与强化了活性污 泥的絮体结构， 形成了具有较高反应活性与絮体稳定性的硝化功能活性污泥， 最终活性污泥 混合液在二沉池内进行泥水分离， 分离后活性污泥上清液进行进一步处理或排放。 The invention directly feeds fresh un-aged iron hydroxide prepared on site into an aerobic tank in a sewage biological nitrogen removal system, and strengthens iron by combining iron hydroxide flocs with activated sludge microbial flocs. Ions participate in the interaction of electron transport and enzymatic activator, which not only effectively enhances the biochemical reaction metabolic activity of microorganisms, but also improves and strengthens the floc structure of activated sludge, forming nitrification with high reactivity and floc stability. Functional activated sludge, the final activated sludge mixture is separated into muddy water in the secondary settling tank, and the activated sludge supernatant is separated for further treatment or discharge.
在污水生物脱氮***设施 （该污水生物脱氮***是指硝化功能微生物巳经处于稳定运行 状态或硝化功能微生物具有正常硝化功能的污水生物脱氮***） 现场以三氯化铁和碳酸氢钠 为原料制备浓度为 10%的超微粒氢氧化铁溶液的过程如下： In the sewage biological nitrogen removal system facility (the sewage biological nitrogen removal system refers to the nitrification function microorganisms in the stable operation state or the nitrification function microorganisms have the normal nitrification function of the sewage biological nitrogen removal system) on the site with ferric chloride and sodium bicarbonate The process for preparing an ultrafine iron hydroxide solution having a concentration of 10% as a raw material is as follows:
为有效控制三氯化铁与碳酸氢钠化学反应强度， 需将三氯化铁溶液浓度和碳酸氢钠溶液 浓度分别控制在 15%与 2. 6%以内。为此，分别配置质量浓度为 15%与 2. 6%的三氯化铁溶液（水 溶液） 和碳酸氢钠溶液 （水溶液） ， 通过输送管道使三氯化铁溶液和碳酸氢钠溶液同时进入 运行的离心泵 7 (参见图 1 )中，可以通过计量泵精确输送输送三氯化铁溶液或碳酸氢钠溶液， 三氯化铁溶液和碳酸氢钠溶液进入离心泵 7的比例为体积比 1 : 9，液体流速不小于 1. 0米 /秒。 三氯化铁溶液和碳酸氢钠溶液的输送管道的管径可以结合计量泵的参数、 三氯化铁溶液和碳 酸氢钠溶液的比例以及流速确定。 三氯化铁溶液和碳酸氢钠溶液在离心泵内通过离心泵叶轮 的搅拌混合产生化学反应， 生成质量浓度为 10%的超微粒氢氧化铁溶液， 生成的超微粒氢氧 化铁溶液由离心泵 7的出口连续排出。 In order to effectively control the chemical reaction intensity of ferric chloride and sodium bicarbonate, the concentration of ferric chloride solution and the concentration of sodium bicarbonate solution should be controlled within 15% and 2.6%, respectively. For this purpose, a ferric chloride solution (aqueous solution) and a sodium hydrogencarbonate solution (aqueous solution) having a mass concentration of 15% and 2.6% were respectively disposed, and the ferric chloride solution and the sodium hydrogencarbonate solution were simultaneously put into operation through a conveying pipe. In the centrifugal pump 7 (see Fig. 1), the ferric chloride solution or the sodium hydrogencarbonate solution can be accurately conveyed by the metering pump, and the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution to the centrifugal pump 7 is a volume ratio of 1: 9, the liquid flow rate is not less than 1. 0 m / sec. The pipe diameter of the ferric chloride solution and the sodium bicarbonate solution can be determined by combining the parameters of the metering pump, the ratio of the ferric chloride solution and the sodium hydrogencarbonate solution, and the flow rate. The ferric chloride solution and the sodium bicarbonate solution are chemically reacted by agitation mixing of the centrifugal pump impeller in a centrifugal pump to form an ultrafine iron hydroxide solution having a mass concentration of 10%, and the resulting ultrafine iron hydroxide solution is formed by a centrifugal pump. The exit of 7 is continuously discharged.
三氯化铁与碳酸氢钠遵循如下化学反应方程式- Ferric chloride and sodium bicarbonate follow the following chemical reaction equation -
FeCl:! + 3NaHC03 = 3NaCl + Fe (0H) 3 I + 3C02 1 。 FeCl :! + 3NaHC0 3 = 3NaCl + Fe (0H) 3 I + 3C0 2 1 .
三氯化铁与碳酸氢钠药剂消耗及氢氧化铁产生量见下表。 The consumption of ferric chloride and sodium bicarbonate and the amount of iron hydroxide produced are shown in the table below.
氢氧化铁具有两性， 但其碱性强于酸性， 新制得的氢氧化铁易溶于无机酸和有机酸， 亦 可溶于热浓碱。 但氢氧化铁经放置或加热过程 （即使是短时间的） 很容易发生性质变化， 表
现为其在酸中的溶解度下降， 特别随着放置时间的延长， 其越难溶于酸。 Ferric hydroxide has amphoteric properties, but its basicity is stronger than acidity. The newly prepared iron hydroxide is easily soluble in inorganic acids and organic acids, and is also soluble in hot concentrated alkali. However, the ferric hydroxide is easily changed in nature after being placed or heated (even for a short period of time). The solubility in the acid is now reduced, especially as the residence time increases, the more difficult it is to dissolve in the acid.
所以本发明采用现场制备方式，避免氢氧化铁制备后存储陈化导致的反应效率下降问题。 利用新生态 Fe (0H) 3胶体具有超强吸附及聚凝的功能， 并通过电中和、 吸附架桥及絮体的卷 扫作用与活性污泥絮体进行结合， 生成具有絮体结构密实、 比重略大于 1. 0的生物絮体与化 学絮体的结合体。 由此提高了活性污泥絮体的絮凝性能， 改善了活性污泥混合液的分离效果。 Therefore, the present invention adopts an on-site preparation method to avoid the problem of a decrease in reaction efficiency caused by storage aging after the preparation of iron hydroxide. The new ecological Fe (0H) 3 colloid has the functions of super-adsorption and coagulation, and combines with the activated sludge flocs through the electric neutralization, adsorption bridging and flocculation of the flocs to form a dense floc structure. , a combination of biological flocs and chemical flocs having a specific gravity slightly larger than 1.0. Thereby, the flocculation performance of the activated sludge flocs is improved, and the separation effect of the activated sludge mixture is improved.
通过上述方法制备的氢氧化铁溶液进行硝化功能微生物的培养， 具体过程如下： 对于污水生物脱氮***而言， 首先保证***内硝化功能微生物处于稳定运行状态， 或经 过连续培养保证***内硝化功能微生物具有正常的硝化功能， 在此基础上， 进行高活性硝化 功能微生物的培养。 将通过三氯化铁 （FeCl3) 与碳酸氢钠 （NaHC03) 化学反应现场制备的超 微粒氢氧化铁 （Fe (0H) 3浓度为 10%) 连续或采用分批次投加方式 （一般为 5〜10批次） 快速 直接投加到生物脱氮***好氧池 3内的活性污泥混合液中， 其投加量控制在活性污泥混合液 含 Fe量为 5mg/g · MLVSS · d〜10mg/g · MLVSS · d， 其投加点根据好氧池反应型式而异， 对于 完全混合式好氧池， 其超微粒氢氧化铁直接投加生物脱氮***好氧池中央部位； 对于推流式 好氧池， 其超微粒氢氧化铁直接投加生物脱氮***好氧池廊道的中前段， 即按照理论水力停 留时间计的活性污泥流经好氧池的时间段为 1. 5h〜2. 5h之间的廊道内，并利用好氧池内的曝 气混合作用实现超微粒氢氧化铁与活性污泥的快速混合。 最终超微粒氢氧化铁（Fe (0H) 3浓度 为 10%)的总投加量控制在活性污泥混合液中含铁量达到 30〜50mgFe/g · MLVSS (混合液挥发 性悬浮固体浓度） 。 在培养过程中保持污水生物脱氮***原有进水负荷条件不变， 逐渐延长 活性污泥泥龄， 使达到满足正常硝化负荷条件的设计泥龄的 1〜2倍， 该培养过程所需时间为 10〜20天。 The iron hydroxide solution prepared by the above method is used for culturing the nitrifying function microorganisms, and the specific process is as follows: For the sewage biological nitrogen removal system, firstly, the nitrification function microorganisms in the system are in a stable operation state, or the continuous nitrification function is ensured by continuous culture. The microorganism has a normal nitrification function, and on the basis of this, a highly active nitrifying microorganism is cultured. Ultrafine iron hydroxide (Fe (0H) 3 concentration of 10%) prepared on site by chemical reaction of ferric chloride (FeCl 3 ) with sodium bicarbonate (NaHC0 3 ) continuously or in batches (usually 5 to 10 batches) are quickly and directly added to the activated sludge mixture in the aerobic tank 3 of the biological nitrogen removal system, and the dosage thereof is controlled in the activated sludge mixture containing Fe amount of 5 mg/g · MLVSS · d~10mg/g · MLVSS · d, the dosing point varies according to the aerobic tank reaction type. For the fully mixed aerobic tank, the ultrafine iron hydroxide is directly added to the central part of the aerobic tank of the biological denitrification system; The push-flow aerobic tank, the ultra-fine iron hydroxide directly is added to the middle and front sections of the aerobic pool corridor of the biological nitrogen removal system, that is, the time period of the activated sludge flowing through the aerobic tank according to the theoretical hydraulic retention time is 1 In the corridor between 5h and 2. 5h, the aerobic mixing in the aerobic tank is used to achieve rapid mixing of the ultrafine iron hydroxide with the activated sludge. The total dosage of the ultrafine iron hydroxide (Fe (0H) 3 concentration of 10%) is controlled to be 30~50mgFe/g in the activated sludge mixture. · MLVSS (mixed liquid volatile suspended solids concentration) . During the cultivation process, the original influent load condition of the sewage biological nitrogen removal system is kept unchanged, and the activated sludge sludge age is gradually extended to reach 1 to 2 times of the design sludge age satisfying the normal nitrification load condition, and the time required for the cultivation process For 10 to 20 days.
本发明的方法包括硝化功能微生物的培养阶段和硝化功能微生物的长期运行活性保持阶 段， 硝化功能微生物培养阶段结束后进入硝化功能微生物的长期运行活性保持阶段。 随着微 生物絮体与氢氧化铁絮体结合体的形成与稳定， 向生物脱氮***好氧池内的活性污泥混合液 中直接投加铁盐化学药剂 （FeCl2、 FeS04 或 FeCl3)， 以补充铁元素的流失量， 铁盐化学药剂 投加点与培养阶段一致， 污水生物脱氮***中每处理一升污水补充投加的铁盐化学药剂中铁 元素的量为 lrag - 2mg， 该投加量仅作为随剩余污泥排放流失铁元素的补充， 具体投加量按照 剩余污泥排放导致的污水生物脱氮***内铁的流失量计算。 此阶段铁离子介入具有脱氮功能 的活性污泥微生物代谢过程， 强化铁离子参与电子传递作用与酶促反应激活剂作用， 能够有 效提高微生物的生化反应代谢活性， 而且对细菌繁殖和酶的分泌有着促进作用， 由此形成具 有较高生物代谢活性的硝化功能活性污泥。 The method of the present invention comprises a culture stage of a nitrifying functional microorganism and a long-term activity maintaining stage of the nitrifying functional microorganism, and the long-term activity maintaining phase of the nitrifying functional microorganism is maintained after the end of the nitrifying functional microbial culture stage. With the formation and stabilization of the combination of microbial flocs and ferric hydroxide flocs, iron salt chemicals (FeCl 2 , FeS0 4 or FeCl 3 ) are directly added to the activated sludge mixture in the aerobic tank of the biological nitrogen removal system. In order to supplement the loss of iron, the iron salt chemical dosage point is consistent with the cultivation stage. The amount of iron in the iron salt chemical added per liter of sewage treated in the sewage biological nitrogen removal system is lag - 2mg, the investment The addition amount is only used as a supplement to the iron element lost from the excess sludge discharge. The specific dosage is calculated according to the amount of iron loss in the biological biological nitrogen removal system caused by the excess sludge discharge. At this stage, iron ions are involved in the metabolic process of activated sludge microorganisms with denitrification function, and strengthen the role of iron ions in electron transfer and enzymatic reaction activators, which can effectively increase the biochemical reaction metabolic activity of microorganisms, and also promote bacterial reproduction and enzyme secretion. It has a promoting effect, thereby forming a nitrifying functional activated sludge with high bio-metabolism activity.
对于污水生物脱氮而言， 上述两个阶段的作用与影响是巨大的， 首先在人工调控下铁离 子介入具有脱氮功能的活性污泥微生物代谢过程， 强化铁离子参与电子传递作用与酶促反应 激活剂作用， 其不仅有效提高微生物的生化反应代谢活性， 而且其改进与强化了活性污泥的 絮体结构， 形成了具有较高反应活性与絮体稳定性的新型活性污泥； 其次， 铁盐是一种很好 的混凝剂， 随*** pH值（碱度） 的变化， 氢氧化铁进一步发生水解与络合反应， 可以生成电 荷不同的络合阳离子或络合阴离子。 其中多核羟基络合物中羟基 (0H)的架桥作用， 可以生成 聚合度为 2〜900的无机高分子物质， 其不仅可以起到强化活性污泥的吸附作用， 而且其能与 多种金属的氢氧化物发生共沉作用， 去除对某些酶产生抑制影响的重金属， 起到对屏蔽生物
反应酶抑制剂的作用， 进一步强化活性污泥的生化反应活性。 For the biological denitrification of sewage, the effects and effects of the above two stages are enormous. Firstly, iron ions are intervened in the activated sludge microbial metabolic process with denitrification function under artificial control, and iron ions are involved in electron transfer and enzymatic promotion. The action activator not only effectively increases the biochemical reaction metabolic activity of the microorganism, but also improves and strengthens the floc structure of the activated sludge, forming a new activated sludge with high reactivity and floc stability; secondly, Iron salt is a good coagulant. As the pH value (alkalinity) of the system changes, the iron hydroxide is further hydrolyzed and complexed to form complex cations or complex anions with different charges. Among them, the bridging action of hydroxyl group (0H) in the polynuclear hydroxy complex can produce an inorganic polymer material having a polymerization degree of 2 to 900, which not only can enhance the adsorption of activated sludge, but also can be combined with various metals. The hydroxide reacts co-precipitation, removes heavy metals that have an inhibitory effect on certain enzymes, and acts as a shielding organism. The action of the reaction enzyme inhibitor further enhances the biochemical reactivity of the activated sludge.
投加氢氧化铁强化后的生物脱氮***的主要工艺设计参数如下表: The main process design parameters of the biological nitrogen removal system after iron hydroxide strengthening are as follows:
通过本发明的实施， 可以达到如下污水处理效果： Through the implementation of the present invention, the following sewage treatment effects can be achieved:
1. 在较低的铁盐投加量下 （l〜2mgFe/L)， ***抗低温能力得到明显增强， 在反应温度 低于 1CTC条件下， ***硝化效率可以保持 70%以上， ***脱氮效率达到 85%以上； 1. Under the lower iron salt dosage (1~2mgFe/L), the system's low temperature resistance is obviously enhanced. Under the reaction temperature lower than 1CTC, the system nitrification efficiency can be maintained above 70%. More than 85%;
2. ***处理负荷显著提高， 容积负荷率较传统生物脱氮***增加 1倍。 2. The system processing load is significantly improved, and the volumetric loading rate is doubled compared to the traditional biological nitrogen removal system.
3. 具有***启动快， 加药方式简单， 投药量低、 运行经济可靠； 3. It has fast system startup, simple dosing method, low dosage and economical and reliable operation;
4. ***抗冲击负荷能力与运行稳定性提高； 4. The system's impact load resistance and operational stability are improved;
5. 剩余污泥量少 （降低 20〜30%)， 降低污泥处理负荷与费用。 5. The amount of excess sludge is small (reduced by 20~30%), which reduces the sludge treatment load and cost.
实验和实践中的结果显示， 本发明的应用效果实现了本发明的目的， 收到了理想的技术 效果。
The results in experiments and in practice show that the application effect of the present invention achieves the object of the present invention, and an ideal technical effect is obtained.
Claims
1. 一种现场制备投加氢氧化铁提高活性污泥内硝化功能微生物活性的方法，包括硝化功能微 生物的培养阶段和硝化功能微生物的长期运行活性保持阶段， 其特征是： 1. A method for on-site preparation and addition of ferric hydroxide to improve the activity of nitrifying functional microorganisms in activated sludge, including a cultivation stage of nitrifying functional microorganisms and a long-term operation activity maintenance stage of nitrifying functional microorganisms, which is characterized by:
( 1 ) 硝化功能微生物培养阶段- 首先以三氯化铁和碳酸氢钠为原料按以下方法在现场制备浓度为 10%的超微粒氢氧化铁： 分别配置质量浓度为 15%与 2. 6%的三氯化铁溶液和碳酸氢钠溶液， 这样的浓度能够有效 控制三氯化铁与碳酸氢钠化学反应的强度， 通过输送管道使三氯化铁溶液和碳酸氢钠溶液同 时进入运转的离心泵中， 三氯化铁溶液和碳酸氢钠溶液进入离心泵的比例为体积比 1 : 9， 三 氯化铁溶液和碳酸氢钠溶液的流速不小于 1. 0米 /秒，三氯化铁溶液和碳酸氢钠溶液在离心泵 内通过离心泵叶轮的搅拌混合产生化学反应， 生成质量浓度为 10%的超微粒氢氧化铁溶液， 生成的超微粒氢氧化铁溶液由离心泵的出口连续排出； (1) Nitrification functional microorganism culture stage - First, use ferric chloride and sodium bicarbonate as raw materials to prepare ultrafine ferric hydroxide with a concentration of 10% on site according to the following method: Configure the mass concentrations to be 15% and 2.6% respectively. Ferric chloride solution and sodium bicarbonate solution. Such a concentration can effectively control the intensity of the chemical reaction between ferric chloride and sodium bicarbonate. The ferric chloride solution and sodium bicarbonate solution can enter the running centrifuge at the same time through the transportation pipeline. In the pump, the ratio of ferric chloride solution and sodium bicarbonate solution entering the centrifugal pump is a volume ratio of 1:9. The flow rate of ferric chloride solution and sodium bicarbonate solution is not less than 1.0 m/s. The solution and the sodium bicarbonate solution are stirred and mixed by the centrifugal pump impeller to produce a chemical reaction in the centrifugal pump, generating an ultrafine particle iron hydroxide solution with a mass concentration of 10%. The generated ultrafine particle iron hydroxide solution is continuously discharged from the outlet of the centrifugal pump. ;
然后将由离心泵的出口连续排出的超微粒氢氧化铁溶液直接投加到生物脱氮***好氧池 内的活性污泥混合液中， 所述污水生物脱氮***是指硝化功能微生物已经处于稳定运行状态 或硝化功能微生物具有正常硝化功能的污水生物脱氮***， 超微粒氢氧化铁溶液投加量控制 在活性污泥混合液含 Fe量为 5mg/g · LVSS · d〜10mg/g · MLVSS · d， 超微粒氢氧化铁溶液投 加点根据好氧池反应型式而异， 对于完全混合式好氧池， 超微粒氢氧化铁溶液直接投加在好 氧池的中央部位， 对于推流式好氧池， 超微粒氢氧化铁直接投加在好氧池廊道的中前段， 即 按照理论水力停留时间计的活性污泥流经好氧池的时间段为 1. 5小时〜 2. 5小时之间的廊道 、 - 内， 并利用好氧池内的曝气混合作用实现超微粒氢氧化铁与活性污泥的快速混合； 最终超微 粒氢氧化铁的总投加量控制在活性污泥混合液中含铁量达到 30〜50mgFe/g · MLVSS; 在培养 过程中保持污水生物脱氮***原有进水负荷条件不变， 逐渐延长活性污泥泥龄， 使达到满足 ' 正常硝化负荷条件的设计泥龄的 1〜2倍， 该培养过程所需时间为 10〜20天; Then the ultrafine ferric hydroxide solution continuously discharged from the outlet of the centrifugal pump is directly added to the activated sludge mixture in the aerobic tank of the biological denitrification system. The biological sewage denitrification system means that the nitrifying functional microorganisms are already in stable operation. In a sewage biological denitrification system with normal nitrification function or nitrification function microorganisms, the dosage of ultrafine ferric hydroxide solution is controlled so that the Fe content of the activated sludge mixture is 5 mg/g · LVSS · d~10 mg/g · MLVSS · d. The dosing point of the ultrafine-particle ferric hydroxide solution varies according to the reaction type of the aerobic pool. For the completely mixed aerobic pool, the ultrafine-particle ferric hydroxide solution is directly added to the central part of the aerobic pool. For the push-flow aerobic pool In the pool, ultrafine ferric hydroxide is directly added to the middle and front section of the aerobic pool corridor, that is, the time period for activated sludge to flow through the aerobic pool according to the theoretical hydraulic retention time is between 1.5 hours and 2.5 hours. In the corridor and inside the aerobic tank, the aeration mixing effect in the aerobic tank is used to achieve rapid mixing of ultrafine ferric hydroxide and activated sludge; the final total dosage of ultrafine ferric hydroxide is controlled to be within the activated sludge mixture. The iron content in the sewage biological denitrification system reaches 30~50mgFe/g·MLVSS; during the cultivation process, the original inlet water load conditions of the sewage biological denitrification system are kept unchanged, and the activated sludge age is gradually extended to achieve a design that meets the normal nitrification load conditions. 1 to 2 times the age of the mud, and the time required for the cultivation process is 10 to 20 days;
( 2 ) 硝化功能微生物培养阶段结束后进入硝化功能微生物的长期运行活性保持阶段， 随 着微生物絮体与氢氧化铁絮体结合体的形成与稳定， 向生物脱氮***好氧池内的活性污泥混 合液中直接投加铁盐化学药剂， 以补充铁元素的流失量， 污水生物脱氮***中每处理一升污 水补充投加的铁盐化学药剂中铁元素的量为 lmg -2mg, 该投加量仅作为随剩余污泥排放流失 铁元素的补充， 具体投加量按照剩余污泥排放导致的污水生物脱氮***内铁元素的流失量计 算； 此阶段铁离子介入具有脱氮功能的活性污泥微生物代谢过程， 强化铁离子参与电子传递 作用与酶促反应激活剂作用， 能够有效提高微生物的生化反应代谢活性， 而且对细菌繁殖和 酶的分泌有着促进作用， 由此形成具有较高生物代谢活性的硝化功能活性污泥。
(2) After the cultivation phase of nitrifying functional microorganisms, the long-term operation activity maintenance phase of nitrifying functional microorganisms enters. With the formation and stabilization of the combination of microbial flocs and iron hydroxide flocs, the active wastewater in the aerobic tank of the biological denitrification system Iron salt chemicals are added directly to the mud mixture to supplement the loss of iron. The amount of iron in the iron salt chemicals added per liter of sewage treated in the sewage biological denitrification system is 1mg -2mg. The dosage is only used to supplement the iron lost with the discharge of remaining sludge. The specific dosage is calculated based on the loss of iron in the sewage biological denitrification system caused by the discharge of remaining sludge. At this stage, iron ions intervene in the activity with denitrification function. The sludge microbial metabolism process strengthens the participation of iron ions in electron transfer and enzymatic reaction activator, which can effectively improve the biochemical reaction metabolic activity of microorganisms, and promote bacterial reproduction and enzyme secretion, thus forming a high biological Metabolically active nitrification functional activated sludge.
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| JP2020030227A (en) * | 2018-08-20 | 2020-02-27 | 三菱瓦斯化学株式会社 | Film-forming material for lithography, film-forming composition for lithography, underlay film for lithography and patterning method |
| JP7258279B2 (en) | 2018-08-20 | 2023-04-17 | 三菱瓦斯化学株式会社 | Film-forming material for lithography, film-forming composition for lithography, underlayer film for lithography, and pattern forming method |
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| CN102502949A (en) | 2012-06-20 |
| CN102502949B (en) | 2013-06-12 |
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