WO2005035448A1 - Procede de purification d'eaux usees - Google Patents

Procede de purification d'eaux usees Download PDF

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Publication number
WO2005035448A1
WO2005035448A1 PCT/FI2004/000566 FI2004000566W WO2005035448A1 WO 2005035448 A1 WO2005035448 A1 WO 2005035448A1 FI 2004000566 W FI2004000566 W FI 2004000566W WO 2005035448 A1 WO2005035448 A1 WO 2005035448A1
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WO
WIPO (PCT)
Prior art keywords
waste water
coagulant
flocculation
process according
biofilm reactor
Prior art date
Application number
PCT/FI2004/000566
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English (en)
Inventor
Hallvard ØDEGAARD
Donald Jonasson
Timo Kenakkala
Jukka Jokela
Mika Christophliemk
Vesa Hietapelto
Original Assignee
Kemira Oyj
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kemira Oyj filed Critical Kemira Oyj
Publication of WO2005035448A1 publication Critical patent/WO2005035448A1/fr

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Classifications

    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

Definitions

  • the present invention relates to a process for purification of waste water comprising pre-treatment, biological treatment in a biofilm reactor, coagulation, flocculation and floe separation.
  • the principle behind the high-rate treatment concept is that coagulation, flocculation and flotation is used to separate suspended and colloidal matter, including biomass, while a high-rate moving bed biofilm reactor (MBBR) is used for removing easily biodegradable, soluble matter, that produces biomass.
  • MBBR moving bed biofilm reactor
  • Combined low doses of metal coagulant and cationic polymer added separately are used to achieve a cost effective particle separation process with minimal sludge production.
  • Laboratory-scale experiments demonstrated that good particle removal from a high-rate MBBR effluent was achieved by flotation using a cationic polymer and iron added separately (Melin E. et al., Chemical Water and Wastewater Treatment VII, pp. 261-271, 2002, IWA Publishing, London).
  • GB 1 512 022 discloses a flocculating agent for water treatment comprising a concentrated aqueous solution of an inorganic flocculating agent and an organic cationic polymer.
  • the inorganic flocculating agent comprises ferric sulphate, ferrous sulphate, aluminium chlorohydrate, aluminium sulphate or ferric chloride, and the organic cationic polymer is for example a polyvinyl pyridine, a polyamide, a polyamine or a polyalkyleneimine.
  • the flocculating agent is fed into a stream of an aqueous suspension of solid material causing formation and precipitation of a hydroxide corresponding to the inorganic flocculating agent.
  • the amount of the inorganic flocculating agent is equal to or greater than the amount of the cationic polymer.
  • the high amounts of the inorganic flocculating agent results in the formation of high amounts of sludge (iron or aluminium hydroxide) which is unfavourable in view of the further treament of the sludge.
  • GB 2 322 128 A discloses a coagulant for clarifying drinking water.
  • This coagulant is formed by the reaction of an inorganic coagulant with a cationic polymer at elevated temperature, typically at a temperature in the range of 45-65°C.
  • the inorganic coagulant is aluminium sulphate, ferric chloride, aluminium polyhydroxy- chlorosulphate or ferric sulphate, and the cationic polymer is obtained by polymerization of vinyl monomers such as diallyl dimethyl ammonium chloride.
  • the amount of the polymer in relation to the inorganic coagulant is very small, and the amount of the polymer in the final product is also very small, typically 0.5% or 1 % of the total weight of the final product.
  • This coagulant is exclusively designed for the clarification of raw water (contaning minor amounts of organic substances, such as humic acids, and cations and anions) in drinking water treatment plants.
  • KR 2000059008 A discloses combined removal agents for coloring agents and COD in dyeing wastewater using decoloration and agglomeration. These combined removal agents are composed of a cationic polymer decolorant, a stabilizing agent and a coagulant, such as Fe(lll) and alum.
  • the polmer is made from dicyandiamide, ammonium chloride and formalin. According to this document there is no reaction between the cationic polymer and the inorganic compounds.
  • GB 2 296 238 A discloses a composition for removal of dyes from textile industry effluents comprising a ferrous salt, a polyamine or a diallyldialkylammonium polymer (polydadmac) and a dicyandiamide-formaldehyde-ammonium chloride. These three components are added either as a blend or individually. This composition is claimed to provide a synergistic effect, and removing the final brown colour from the effluent.
  • WO 03/029151 A1 discloses a composition for use as a coagulation and flocculating agent in the purification of waste water.
  • the disclosed composition consists of an aqueous solution of polyaluminium chloride as the main constituent, a magnesium or calcium compound and an organic polymer flocculating agent.
  • the organic flocculating agent is a polyamine, a poly-diallyldimethyl-ammonium chloride, a polyethylenimine acetate or a polyethylenimine.
  • the amount of the organic flocculating agent is preferably 20-25 parts by weight per 100 parts by weight of aluminium.
  • US 4 891 422 discloses inorganic-organic alloy polymer adduct compositions for purification of potable water, paper mill effluent or industrial waste water.
  • the adduct composition is made from an inorganic polymer in reaction with a guanidine polymer or an organic alloy thereof with a polyamine, polyquaternized polymer, polyamide or polyamine-polyamide polymer.
  • the ratio of the polymer(s) to the metal(s) is typically very high, i.e. the amount of the metal is small in comparison to the amount of the polymer.
  • the preferred metal component seems to be aluminium.
  • GB 1 424 702 discloses a method of decolorizing waste colored aqueous liquid containing non-cationic coloring substance with a water-soluble organic coagulating agent or a metallized complex of said organic coagulant.
  • the organic coagulant is a condensation product of for example a polyamine compound with an aldehyde, or an aromatic amino compound with an aldehyde or a mixture of two amino compounds with an aldehyde. Copper ion is most valuable in obtaining the metallized coagulating agent.
  • the present invention is focussed on the purification of municipal waste waters and normal industrial waste waters especially from food industry or forest industry.
  • the major part of the organic loading from municipal waste water is particulate organic matter having a specific particle size distribution.
  • the soluble organic matter can be well represented by organic matter found in particle sizes less than 0.1 ⁇ m whereas the colloids and suspended solids typically have a particle size of above 0.1 ⁇ m.
  • the municipal waste waters contain dissolved nutrients, for instance phosphorous that is of main interest.
  • the object of the present invention is to provide a compact, high-rate waste water treatment process, which provides a good purification efficiency, particularly with respect to suspended solids, organic matter and phosphorous, is easy to control and produces a low amount of sludge, particularly metal hydroxide sludge.
  • a process for purification of waste water comprising a pre-treatment to obtain a pretreated waste water, subjecting the pretreated waste water to a biological treatment in a biofilm reactor, followed by coagulation, flocculation and floe separation, said flocculation being induced by a coagulant in the form of a complex comprising an inorganic divalent or trivalent metal moiety and an organic polymer moiety.
  • Said pre-treatment can be a physical (sieving, settling etc) or chemical or physical/chemical pre-treatment.
  • the physical pre-treatment comprises removing large particles from the waste water by a sieve, preferably with sieve openings ⁇ 0,5 mm.
  • a preferred biofilm reactor comprises a high-rate biofilm reactor, preferably a moving bed biofilm reactor (MBBR).
  • MBBR moving bed biofilm reactor
  • the hydraulic retention time (HRT) in the MBBR is adapted so as to minimize the hydrolysis of particulate organic matter including colloids and solid substances, the HRT being preferably from 15 to 60 minutes, and more preferably from 30 to 45 minutes, when municipal waste water is treated.
  • the soluble organic matter is removed by means of the biological treatment in the biofilm reactor, preferably in the MBBR, and particulate organic matter including colloids and suspended solids including biomass produced in the biological treatment is removed by means of said coagulation/flocculation/separation.
  • the soluble organic matter typically has a particle size of below 0.1 ⁇ m, and the particulate organic matter including colloids and suspended solids typically has a particle size of above 0.1 ⁇ m.
  • the process of the invention preferably includes a flocculation between the biofilm reactor and the floe separation.
  • the flocculation is preferably carried out in a flocculation tank.
  • the hydraulic overflow rate is preferably from 5 to 20 m 3 /m 2 h, more preferably from 7.5 to 10 m 3 /m 2 h.
  • the HRT in the flocculation tank is preferably from 5 to 15 minutes, more preferably from 7.5 to 10 minutes.
  • the floe separation is preferably carried out by means of flotation. Dissolved air flotation is especially preferred.
  • the hydraulic overflow rate in the flotation tank is preferably from 5 to 20 m 3 /m 2 h, more preferably 7.5 to 10 m 3 /m 2 h.
  • the HRT in the flotation is preferably from 10 to 30 minutes, more preferably from 15 to 25 minutes. It is also possible to carry out the floe separation by other per se known methods, such as sedimentation or filtration.
  • the waste water to be purified by the process of the invention can be industrial waste water, for example from food industry or forest industry, or municipal waste water or a combination thereof.
  • the metal complexed polymer coagulant of the invention can operate at pH values between 2 and 9.
  • the pH of normal municipal waste water is typically between 5 and 8.
  • the complexed coagulant is preferably added to the waste water after the biofilm reactor. It is also possible to add the complexed coagulant into or before the biofilm reactor.
  • the coagulant is preferably added in an amount of 100 to 600 mg/g SS (suspended solids), more preferably 200 to 350 mg/g SS in the waste water to be treated (preferably after the biofilm reactor), calculated on the basis of dry content of the coagulant.
  • the coagulant is preferably added in an amount per litre of 0.2 to 1.1 mg/NTU (Nephelometric Unit), more preferably 0.6 to 1.0 mg/NTU in the waste water to be treated, calculated on the basis of dry content of the coagulant.
  • NTU Nephelometric Unit
  • Said organic polymer can be selected from the group consisting of
  • Said organic polymer can also comprise the reaction or condensation products of two or more of these polymers or condensation products.
  • a preferred organic polymer comprises a polymer made from formaldehyde, dicyandiamide and ammonium chloride.
  • Said divalent or trivalent metal can be divalent or trivalent iron, trivalent aluminum or divalent copper, preferably trivalent iron.
  • a preferred metal complexed polymer coagulant is an Fe 3+ -complexed dicyandiamide-ammonium chloride polymer.
  • the weight ratio of the organic polymer moiety to the inorganic moiety is preferably in the range from 7:1 to 3:1 , more preferably from 6:1 to 4:1 , for example about 5:1.
  • the metal complexed polymer coagulant is water soluble and cationic.
  • the metal complexed polymer coagulant is preferably added to the waste water in the form of an aqueous solution.
  • the metal complexed coagulant can be obtained by reacting an organic polymer capable of forming a complex with a divalent or trivalent metal, and a source of a bivalent or trivalent metal in an aquous solution at a temperature of between 0°C and 45°C, preferably between 10°C and 30°C, and more preferably between 15°C and 25°C.
  • a temperature of between 0°C and 45°C preferably between 10°C and 30°C, and more preferably between 15°C and 25°C.
  • the source of the bivalent or trivalent metal can be a sulphate or chloride of said metal, for example ferric chloride, ferric sulphate, ferrous sulphate, aluminium sulphate (alum), aluminium chloride, hydroxyaluminium chloride, hydroxyaluminium sulphate, cupric sulphate or cupric chloride.
  • ferric chloride ferric sulphate, ferrous sulphate, aluminium sulphate (alum), aluminium chloride, hydroxyaluminium chloride, hydroxyaluminium sulphate, cupric sulphate or cupric chloride.
  • the above metal salts can be in solid form or in the form of an aqueous solution.
  • the aqueous solution can be a concentrated solution of the metal salt.
  • the process of the present invention removes very efficiently organic substances and phosphorous present in waste waters.
  • the soluble organic matter is removed by the biological treatment in the biofilm reactor and the particulate organic matter including colloids and suspended solids including biomass produced during biological treatment are removed by means of the treatment with the coagulant followed by flocculation and floe separation.
  • metal hydroxides such as iron hydroxides (i.e. amount of sludge) during the purification of waste waters, such as municipal waste water is expected to be low.
  • An advantage of the metal complexed polymer coagulant used in the process of the invention is that due to the optimal proportion of the polymer and metal in the complexed polymer coagulant, the amount of the metal hydroxide sludge will be very small and the precipitated sludge will have good dewatering ability facilitating the further treatment of the sludge, including for example dewatering and burning. Upon burning the sludge the ash content will be low.
  • the sludge is also suitable for composting or as a land filling substance. Also the floes are densely packed in the sludge whereby the volume of the sludge is small.
  • the metal complexed coagulant used in the process of the present invention provides the advantages of being easier to handle, dose and control.
  • Fig. 1 shows results of sedimentation tests obtained by using an Fe 3+ -complexed DCD polymer coagulant of the invention and a reference DCD polymer coagulant.
  • An aqueous DCD polymer solution (prepared from formaldehyde, dicyandiamide and ammonium chloride) was used as starting material.
  • the Fe 3+ -complexed DCD polymer coagulant is made by adding grinded FeCI 3 -6H 2 0 (1 g) gradually into the DCD polymer solution (2g) and stirring the solution for 30 minutes as the iron dissolved at room temperature. A portion of the obtained coagulant (0.2 g) dissolved in 30ml distilled water was titrated by concentrated NaHC0 3 solution and the pH was monitored. A precipitate was formed at pH ⁇ 6.8-7.0. From a pure Fe(lll) solution iron hydroxide precipitates at pH ⁇ 4. The complex formation between the trivalent iron and the DCD polymer prevents the precipitation of iron hydroxides below pH ⁇ 7. As compared to the DCD polymer the Fe 3+ -complexed DCD polymer of the invention has an increased cationic charge density in the molecule.
  • test results show that the turbidity decreases noticeably, when the waste water is treated with the Fe 3+ -complexed DCD polymer of the invention. This is due to the increased cationic charge density in the molecule.
  • the reference DCD polymer was much less effective.
  • the tests were carried out using a laboratory-scale flotation tester.
  • Clarified water was analysed for suspended solids (SS) using GF/C filter, turbidity, chemical oxygen demand (COD), and filtered COD (FCOD) (filtered through GF/C filter having nominal pore size of 1.2 ⁇ m). Dry solids (DC) and volatile solids (VS) were analysed from the sludge samples.
  • SS suspended solids
  • COD chemical oxygen demand
  • FCOD filtered COD
  • Tests were carried out in order to investigate a compact waste water treatment process.
  • the process combines a moving bed biofilm reactor (MBBR) with low- dose coagulation and flocculation/flotation.
  • MBBR moving bed biofilm reactor
  • Waste water was taken from Ladehammer waste water plant in Trondheim, Norway. The plant receives both municipal and food industry waste water. The waste water was taken from the pilot plant influent.
  • the Fe 3+ -complexed DCD polymer (DCD+Fe) prepared in Example 1 was used as coagulant.
  • the sludge layer stayed in the jar and was then washed out by distilled water into sample bottles.
  • the coagulant (DCD+Fe) was tested at doses of 75, 125 and 200 ⁇ l/l. The doses are given as pure product but the dosing solution was diluted 1 :10 since the sample had quite high viscosity.
  • the process performance was evaluated by taking samples from raw waste water (after sieve), MBBR effluent and flotation outlet. The samples were analysed for suspended solids (SS) using GF/C filter, turbidity, chemical oxygen demand (COD), and filtered COD (FCOD) (filtered through GF/C filter having nominal pore size of 1.2 ⁇ m). Dry solids (DC) and volatile solids (VS) were analysed from the sludge samples.
  • SS suspended solids
  • COD chemical oxygen demand
  • FCOD filtered COD
  • the pilot-plant was located in the Ladehammeren wastewater treatment plant in Trondheim, Norway.
  • the treatment plant receives both municipal and food industry wastewater.
  • the MBBR had a total volume of 5 m 3 .
  • the bioreactor contained Kaldnes K1 biofilm carriers occupying 50% of the reactor volume. This gives an effective surface area of 250 m 2 /m 3 reactor volume.
  • the MBBR effluent flowed into flocculation tank through an overflow tank.
  • the Fe 3+ -complexed DCD polymer (DCD+Fe) prepared in Example 1 was used in the test as 5:8 dilution (5 parts product and 3 parts water) and dosed with an in-line mixer.
  • the flocculation consisted of two chambers fitted with turbine mixers and had a total volume of 2.5 m 3 .
  • the flocculation tank was connected to a 1.4 m 3 flotation unit (surface area of 1 m 2 ).
  • the flow to flotation was initially 5 m 3 /h but was decreased to 4 m 3 /h for documentation period resulting in 20% and 30% recycle ratios, respectively.
  • the plant was equipped with on-line sensors for suspended solids measurement from the MBBR and flotation effluents.
  • the standard flocculation tank in the pilot plant was larger than required, some experiments were carried out with a more compact flocculation unit.
  • a pipe flocculator was installed inside the standard flocculation tank.
  • the compact flocculation had a volume of 0.44 m 3 and had 300 vertical pipes with inner diameter of 28 mm and length of 1 m.
  • the process performance was evaluated by taking composite samples over 24 hours period from raw water (after sieve), MBBR effluent and flotation outlet. The samples were analysed for suspended solids (SS), chemical oxygen demand (COD) filtered COD (FCOD), biological oxygen demand (BOD5), filtered BOD5 (FBOD5) and total phosphorus. GF/C filters with nominal pore size of 1.2 ⁇ m were used in SS, FCOD and FBOD analyses. In some tests, composite samples taken over shorter periods of time were also analysed to study the effect of wastewater variation on the process.
  • the sludge formation studies were carried out over a two hours period.
  • the floating sludge was removed at 30 min intervals and collected into a sludge tank.
  • the volume of the sludge was measured together with dry solids (DS) content.
  • SS samples were collected from the MBBR and flotation effluents.
  • the specific sludge production SSremoved/DSformed could then be calculated for the chemical treatment of the MBBR effluent.
  • the MBBR was operated with a HRT of 60 minutes.
  • Table 5 shows the average and max/min influent waste water quality in the tests.
  • the SS concentration in flotation effluent was below 15 mg/l and SS-removal efficiencies above 92 % at a dosing range from 22 to 89 ⁇ l/l. Good removal efficiencies were achieved demonstrating that regulating the coagulant doses improved the treatment results.
  • the total COD concentration in flotation effluent was between 40 mg/l and 125 mg/l when FCOD concentration in MBBR effluent was between 30 mg/l and 150 mg/l, respectively.
  • the results show the importance of soluble organic matter concentrations in the MBBR effluent to the total organic matter removal efficiency in the process.
  • the results demonstrate that good removal of particulate COD and BOD5 was achieved from the MBBR effluent and some FCOD was also removed. The COD and BOD5 removals in the whole process are therefore mainly affected by removal of soluble fractions in the MBBR.
  • the average sludge production was very small, about 1 g DS pr0 **d/g SS rem oved.
  • the iron doses used in the process were low enough to prevent significant excess sludge production due to precipitation.
  • the average dry solids concentration in the sludge was 25 g/l.
  • the results of dewatering tests showed good dewaterability and indicated that about 40 % dry solids content could be reached in dewatered sludge.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

L'invention concerne un procédé de purification d'eaux usées. Ce procédé consiste à effectuer un prétraitement pour obtenir des eaux usées prétraitées, puis à soumettre ces eaux usées prétraitées à un traitement biologique dans un réacteur à biofilm, suivi d'une coagulation, d'une floculation et d'une séparation du floc, ladite floculation étant induite par un coagulant se présentant sous la forme d'un complexe comprenant une partie de métal divalent ou trivalent inorganique et une partie polymère organique.
PCT/FI2004/000566 2003-10-10 2004-09-28 Procede de purification d'eaux usees WO2005035448A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20031484 2003-10-10
FI20031484A FI116566B (fi) 2003-10-10 2003-10-10 Metallikompleksoitu orgaaninen koagulantti jäteveden puhdistamiseksi

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WO2005035448A1 true WO2005035448A1 (fr) 2005-04-21

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PCT/FI2004/000600 WO2005035449A1 (fr) 2003-10-10 2004-10-11 Coagulant organique formant un complexe avec un metal pour purification des eaux usees

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN102060416A (zh) * 2010-12-01 2011-05-18 北京林业大学 一种利用缺氧-好氧移动床生物膜反应器组合工艺处理低温城市污水的方法
CN102190395A (zh) * 2010-03-08 2011-09-21 许国仁 Tf单元组合污水处理工艺
CN102633404A (zh) * 2012-03-16 2012-08-15 山东天畅环保工程有限公司 综合废水处理工艺
US9440890B2 (en) 2010-04-30 2016-09-13 Koch Agronomic Services, Llc Reaction products and methods for making and using same
CN106242185A (zh) * 2016-08-30 2016-12-21 广西福达环保科技有限公司 香蕉浆生产废水处理方法
CN106430556A (zh) * 2016-09-30 2017-02-22 南京大学 一种青霉素废水mbbr处理系统的启动方法
CN106430560A (zh) * 2016-11-29 2017-02-22 南京大学 一种废水生物膜快速挂膜装置及方法
US10125056B2 (en) 2010-04-30 2018-11-13 Koch Agronomic Services, Llc Reaction products and methods for making and using the same
WO2020249863A1 (fr) * 2019-06-10 2020-12-17 Kemira Oyj Procédé d'élimination de composés organiques dissous d'eaux usées
WO2020258749A1 (fr) * 2019-06-24 2020-12-30 齐鲁工业大学 Adsorbant de lignine, son procédé de préparation et son application

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GB2024795A (en) * 1978-07-05 1980-01-16 Sgn Soc Gen Tech Nouvelle Purification of effluent
US20030201225A1 (en) * 2002-04-30 2003-10-30 Josse Juan Carlos Organic slurry treatment process

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CN102190395B (zh) * 2010-03-08 2014-07-02 许国仁 Tf单元组合污水处理工艺
CN102190395A (zh) * 2010-03-08 2011-09-21 许国仁 Tf单元组合污水处理工艺
US10125056B2 (en) 2010-04-30 2018-11-13 Koch Agronomic Services, Llc Reaction products and methods for making and using the same
US11028024B2 (en) 2010-04-30 2021-06-08 Koch Agronomic Services, Llc Reaction products and methods for making and using the same
US9440890B2 (en) 2010-04-30 2016-09-13 Koch Agronomic Services, Llc Reaction products and methods for making and using same
US11148982B2 (en) 2010-04-30 2021-10-19 Koch Agronomic Services, Llc Reaction products and methods for making and using the same
US10239799B2 (en) 2010-04-30 2019-03-26 Koch Agronomic Services Llc Reaction products and methods for making and using the same
CN102060416A (zh) * 2010-12-01 2011-05-18 北京林业大学 一种利用缺氧-好氧移动床生物膜反应器组合工艺处理低温城市污水的方法
CN102633404A (zh) * 2012-03-16 2012-08-15 山东天畅环保工程有限公司 综合废水处理工艺
CN106242185A (zh) * 2016-08-30 2016-12-21 广西福达环保科技有限公司 香蕉浆生产废水处理方法
CN106242185B (zh) * 2016-08-30 2019-04-26 广西福达环保科技有限公司 香蕉浆生产废水处理方法
CN106430556A (zh) * 2016-09-30 2017-02-22 南京大学 一种青霉素废水mbbr处理系统的启动方法
CN106430556B (zh) * 2016-09-30 2019-08-06 南京大学 一种青霉素废水mbbr处理系统的启动方法
CN106430560B (zh) * 2016-11-29 2019-10-11 南京大学 一种废水生物膜快速挂膜装置及方法
CN106430560A (zh) * 2016-11-29 2017-02-22 南京大学 一种废水生物膜快速挂膜装置及方法
WO2020249863A1 (fr) * 2019-06-10 2020-12-17 Kemira Oyj Procédé d'élimination de composés organiques dissous d'eaux usées
WO2020258749A1 (fr) * 2019-06-24 2020-12-30 齐鲁工业大学 Adsorbant de lignine, son procédé de préparation et son application

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