KR101809127B1 - Anammox reactor containing polyketone membrane and method for treating wastewater using the same - Google Patents

Abstract

The present invention relates to an anammox reaction tank and a method for treating wastewater using the same. More specifically, the present invention relates to an anaerobic bioreactor that can economically remove organic matter and nitrogen contained in wastewater by using a membrane made of polyketone, The effective removal of dissolved contaminants can improve the quality of the final effluent.

Description

Anammox reaction tank containing a membrane made of polyketone and a method for treating wastewater using the same

The present invention relates to an Anamx reaction tank and a method for treating wastewater using the same. More particularly, the present invention relates to an Anamx reaction tank that economically removes organic matter and nitrogen contained in wastewater by using a polyketone membrane and simultaneously removes particulate matter and dissolved contaminants Thereby effectively improving the quality of the final effluent by removing the effluent.

The causes of water pollution include organic matter and minerals such as nitrogen and phosphorus. Nitrogen is one of the nutrients, which causes eutrophication and red tide, promotes the generation of harmful living organisms, increases the chemical oxygen demand, and organic matter should be removed because it reduces the amount of dissolved oxygen in the water system.

As a method of treating wastewater containing various pollutants, the metabolism of aquatic microorganisms is utilized.

Typical wastewater treatment methods are decomposition and treatment of organic matter in wastewater using aerobic microorganisms in a reaction tank. However, the conventional wastewater treatment method has a disadvantage in that a large amount of power is required for operation of an oxidant or blower for supplying air into the reaction tank. In Korea, it is known that about 40% of the total power consumption of the sewage treatment plant is consumed in the operation of the blower. In addition, nitrogen in wastewater is generally removed by nitrification / denitrification (heterotrophic denitrification) processes (eg, MLE, A2O processes, etc.).

However, in the case of removing nitrogen by a general nitrification / denitrification process, it is necessary to supply a large amount of air to nitrify ammonia with nitrate. In case of denitrification, an organic matter is required and an organic matter is additionally added. At the same time, a large amount of sludge is generated There is a problem that the cost increases.

To solve this problem, the proposed nitrogen removal process is the Anamox process. This is because the nitrogen is removed by reacting ammonia and nitrite to generate nitrogen gas, which can reduce the power consumption required for ammonia oxidation, does not require addition of organic matter, and can reduce the amount of sludge generated compared to a general nitrification / denitrification process It is very economical.

However, since the growth rate of the anammox microorganism is slow, it is necessary to continuously maintain the microorganism in the reaction tank for a long time. Maintaining the concentration of microorganisms in these reaction vessels is very important in the Anammox process, especially when the microbial loss occurs in the reaction tank. Therefore, the Anammox process has only been applied to the treatment of high concentrations of nitrogen wastewater, and it is a reality that there are few applications at low concentrations.

Korean Registered Patent No. 1371220

The present invention relates to a method and apparatus for simultaneously removing organic matter and nitrogen in a reaction tank by using a polyketone membrane reaction tank and removing particulate matter and some dissolved contaminants which are not removed by a biological reaction, And to provide a method for removing the same.

In order to solve the above-mentioned problems, the present invention provides a biosensor comprising a reaction tank body containing anammox microorganisms; Fluidized particles flowing in the reaction tank body with an anomaly microorganism attached thereto; A gas-flowing particle separator provided at an upper portion of the reactor body; A membrane made of polyketone which removes particulate matter and dissolved contaminants in the effluent water immersed in the reaction tank body and not removed by microorganisms; A circulation unit for circulating the effluent in the reaction tank body; An air supply unit for supplying / adjusting dissolved oxygen at a low concentration required for the anammox process in the reaction vessel main body; And an outflow pump connected to the membrane to discharge the effluent in the reaction tank body to the outside.

The polyketone membrane of the present invention is formed of a hollow fiber membrane or a flat membrane having a plurality of micropores. The polyketone used as the membrane of the present invention is a copolymer of carbon monoxide and ethylene copolymer or a terpolymer obtained by copolymerizing carbon monoxide, ethylene and propylene.

In the present invention, a portion of ammonia is oxidized into nitrite by maintaining a low concentration of dissolved oxygen (that is, about 0.1 to 0.3 mg / L) in the simultaneous removal of nitrogen and organic substances in the wastewater by using a polyketone membrane reaction tank, It is possible to greatly reduce power consumption for supplying air necessary for oxidizing ammonia, and it is unnecessary to add organic matter for nitrogen removal, the amount of sludge generated is smaller than that of the conventional process, The organic matter remaining in the influent wastewater is consumed and treated for reducing nitrite, which is a by-product of the nitrite process or the by-product of the anamox process, to nitrogen gas, thereby improving water quality.

1 is a view showing a main part of a wastewater treatment system for implementing a method of simultaneously removing nitrogen and organic substances from wastewater using an Anammox reaction tank

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

While the present invention has been described with reference to certain embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and similarities. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular presentation includes plural representations unless the context clearly dictates otherwise

The anammox reaction tank of the present invention comprises a reaction tank body containing anammox microorganisms, a fluidized particle flowing inside the reaction tank body with an anammox microorganism attached thereto, a gas-flowing particle separation portion provided on the reaction tank body, A membrane for removing particulate matter and dissolved contaminants from the effluent water immersed in the effluent water that has not been removed by the microorganisms, a circulation unit for circulating the effluent in the reaction vessel body, a low concentration dissolved oxygen required for the anammox process inside the reaction vessel body And an outflow pump connected to the membrane for discharging the effluent in the reaction tank body to the outside.

The flowable particles act to control the clogging of the membrane by contacting the support medium for the anammox microorganisms and the membrane and removing the accumulated particles on the surface thereof. As such fluidized particles, granular activated carbon (GAC) .

In the present invention, a polyketone membrane using the membrane as a polyketone material is used.

On the other hand, the gas-fluidized particle separation unit is provided with an oil-loss prevention device for preventing the fluidized particles flowing in the reaction tank body from being lost. If necessary, a second gas-fluidized particle separator may be connected to the gas-fluidized particle separator. The second gas-fluidized particle separator may be provided with a second fluid-loss preventing device for preventing the fluidized particles from flowing in the reaction tank.

A gas discharge pipe for discharging the gas generated in the reaction tank body to the outside is connected to the gas-flowing particle separation unit, and a water level sensor for detecting the water level of the reaction tank body is installed.

The control unit controls the operation of the waste water transfer pump according to the water level detection signal in the reaction tank body by the water level sensor to appropriately adjust the amount of wastewater flowing into the reaction tank body.

Meanwhile, the polyketone membrane may be formed of a hollow fiber membrane or a flat membrane having a plurality of micropores. The micropores filter the contaminant particles in the effluent water by passing the effluent but not passing other particulate contaminants Remove.

In addition, since the microorganisms involved in the anammox process in the effluent water remain in the fluidized bed separation membrane Anamox reaction tank, the problem caused by the microbial loss known as the weakest point of the anammox process can be solved. In addition, since the Anammox process is used, the amount of sludge generated is much smaller than that of the conventional heterotrophic denitrification process, and other microorganisms have a very long residence time. Therefore, the amount of sludge generated is minimized, have.

The circulation unit circulates the effluent in the reactor main body. In the lower part of the reactor main body, the gas-flowing particle separator (in the case of the second gas-fluidized particle separator, A circulation line for connecting the fluidized particle separation unit, a circulation pump installed in the circulation line, and a flowmeter. A waste water transfer pump is connected to the circulation line to supply waste water to the circulation unit.

The wastewater transferred by the wastewater transfer pump is transferred along the circulation line as the circulation pump is driven and flows from the lower portion of the reactor main body to cause fluid flow in the reactor main body, Flow upward. Here, the flowing particles flow in balance with the upward velocity of the fluid flowing around the particles, and remain in the reaction vessel body without being lost by the loss prevention device installed in the gas-fluidized particle separation portion.

The simultaneous removal of nitrogen and organic substances from wastewater using a membrane reactor using the above system is as follows.

Transferring the wastewater to a fluid bed membrane anammox reactor by a wastewater transfer pump; Removing nitrogen in the wastewater by using a microorganism staying in the fluid bed separation membrane Anamox reaction tank; And removing the particulate matter and dissolved contaminants in the wastewater by using a polyketone membrane immersed in the fluid bed separation membrane Anamox reaction tank, wherein air is supplied to the fluid bed separation membrane Anamox reactor Supplying / adjusting a low concentration of dissolved oxygen; And discharging the wastewater from which the pollutants have been removed to the outside through an outflow pump.

Specifically, the wastewater is transferred to the liquid phase separation membrane anammosis reactor by the wastewater transfer pump, and the wastewater stored in the reactor body flows by the circulation unit, and processes such as biological reaction and contaminant filtering as described later are performed.

Specifically, the nitrogen in the fluid bed separation membrane Anamox reaction tank is partially nitrified with nitrite and then removed by the anammox process. The organic matter in the influent water is used for denitrification of nitrite and nitrate, or partially removed by oxidation, The particulate phase and dissolved contaminants in the effluent that are not filtered out are filtered out by the polyketone membrane of the present invention.

Meanwhile, dissolved oxygen is injected from the air supply unit in order to form a low-concentration dissolved oxygen atmosphere necessary for the anammox process. In order to filter the particulate contaminants by the membrane, the outflow pump is connected to the reaction vessel body through a membrane, Thereby discharging the waste water.

That is, the simultaneous removal of nitrogen and organic substances from the wastewater using the reaction tank including the polyketone membrane of the present invention can be performed by using a fluidized bed separation membrane Anamox reaction tank to remove nitrogen and organic substances from the wastewater, The action of removing particulate matter and dissolved contaminants in the effluent water takes place almost at the same time, and the wastewater is purified.

In the present invention, a polyketone material is used as the membrane, and preferred polyketones have monomer units alternately arranged. That is, when the polymer is composed of units represented by the general formula - (CO) -A '- (wherein A' represents a monomer unit derived from the applied monomer A) and contains at least one olefinically unsaturated compound (represented simply by A) Molecular weight linear polymers can be prepared by contacting the monomers with a solution of a palladium-containing catalyst composition in a dilute solution in which the polymer is insoluble or substantially insoluble. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.

The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization of the polyketone proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.

In the present invention, as a liquid medium used for polyketone polymerization, a mixed solvent composed of acetic acid and water as well as methanol, propanol, and isopropanol can be used as well as methanol, dichloromethane, or nitromethane, have. Particularly, when a mixed solvent of acetic acid and water is used as a liquid medium in the production of polyketone, the catalyst activity can be improved while reducing the production cost of polyketone. Further, since the use of methanol or a dichloromethane solvent forms a mechanism for causing a stopping reaction during the polymerization step, the use of acetic acid or water other than methanol or dichloromethane in the solvent does not have an effect of stopping the catalytic activity stochastically, It plays a big role in improvement.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the activity is less affected by the catalytic activity, but when the concentration is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, It is most preferable to use palladium acetate.

Examples of ligands (b) having a Group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) Bis [di (2-methylphenyl) phosphino] propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine, ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) Bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) ) Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

The ligand (b) having a group 15 atom preferred in the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, is 1,3-bis- [di (2-methoxyphenyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and more preferably 1,3-bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- ) Phosphine) is better.

[Chemical Formula 1]

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

  In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

In particular, the anion (c) of the acid having a pKa of 4 or less, which is preferred in the present invention, is p-toluenesulfonic acid. When used together with a mixed solvent of acetic acid and water as a liquid medium, It is possible to prepare a polyketone having a functional group

The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.

The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.

In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, C2-C20 alpha-olefins including hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 5 mol% or more than 95 mol%, the reactivity is poor and the physical properties of the produced polyketone may be deteriorated.

The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene or a second olefinically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

In one embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and it is preferable that y / x is 0.01 or less. When the value of the y / x value exceeds 0.01, the mechanical properties are deteriorated.

- [- CH2CH2-CO] x- (1)

- [- CH2 --CH (CH3) - CO] y - (2)

On the other hand, the total melting point of the polymer used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, and preferably 5.0 dl / g to 7.0 dl / g . When the intrinsic viscosity of the polyketone polymer is less than 5.0, the mechanical strength (abrasion resistance) of the separator is lowered. When the intrinsic viscosity is more than 7.0, the workability is deteriorated.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. In the present invention, a mixed solvent of acetic acid and water is used as a liquid medium, and the polymerization reaction is caused by a catalyst composition composed of (a) a palladium compound, (b) a bidentate ligand and (c) an anion of an acid having a pKa of 4 or less , The catalyst is produced by contacting the three components. Any method may be employed. A solution prepared by preliminarily mixing three components in a suitable solvent may be used, or the three components may be supplied to the polymerization system and contacted in the polymerization system.

On the other hand, it is preferable that the molecular weight distribution of the polyketone is 2.5 to 3.5, and if it is less than 2.5, the polymerization yield is lowered. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

In carrying out the present invention, the polymerization method includes a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited and generally 40 to 250 占 폚, preferably 50 to 180 占 폚 is employed. If the reaction temperature is less than 40 ° C, the polymerization reaction is poor and the reaction does not proceed. If the reaction temperature exceeds 250 ° C, a side reaction such as oligomerization or monomer preparation and decomposition reaction is more active than polymerization reaction with a polymer, . The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa. The polymerization reaction rate is very low at a pressure lower than the atmospheric pressure, and the side reaction speed is increased at a pressure of 20 MPa or higher.

Hereinafter, a method for producing a polyketone membrane by preparing a dope using the polyketone will be described.

In the present invention, a dope solution is prepared by dissolving one or more metal salts selected from the group consisting of ZnCl 2, CaCl 2, and LiCl in water as a solvent to prepare a metal salt aqueous solution, and then dissolving the polyketone copolymer in the metal salt aqueous solution . Wherein the aqueous metal salt solution is an aqueous solution of a metal salt selected from the group consisting of ZnCl2 / CaCl2, ZnCl2 / LiCL, ZnCl2 / CaSCN, ZnCl2 / CaCl2 / LiCl and ZnCl2 / CaCl2 / CaSCN.

When the dope solution is prepared, the prepared dope solution is applied on the support to a constant thickness. The dope solution is applied to one side of the support uniformly as the support first passes through a certain distance between the drum and the knife while moving. According to various embodiments of the present invention, in addition to the knife and the drum, the means for applying the dope solution includes a knife and a glass plate, a plate or a drum made of a smooth material having a knife and a surface smoothly processed and a glass plate, a drum and a drum, Extruders and extruders, extruders and drums, extruders and plates of solid material whose surfaces have been smoothly worked.

The support preferably uses polyethylene terephthalate.

The nitrogen and organic matter of the wastewater is removed using the Anamox reaction tank having the above-described structure, and the action of removing particulate matter and dissolved contaminants from the effluent water is almost simultaneously occurred, and the wastewater is purified. Accordingly, it is not necessary to provide a plurality of reaction vessels, and the amount of sludge generated is reduced, so that it is possible to simplify the facilities of the wastewater treatment system such that the facilities for sludge treatment are not provided, .

45, a waste water transfer pump, 51, a reactor main body,
52, flow particles, 53, 53-1, gas-flow particle separator,
54, membrane, 55, circulation unit,
56, an air supply unit 57, an outlet pump,
58, a gas discharge pipe, 59, a water level sensor,
60,

Claims (5)

A reaction tank body containing anammox microorganisms;
Flowing particles in which anammox microorganisms adhere to the inside of the reaction tank body;
A gas-flowing particle separator provided on an upper portion of the reaction vessel body;
A membrane of a polyketone material which removes particulate matter and dissolved contaminants in the effluent water immersed in the reaction tank body and not removed by microorganisms;
A circulation unit for circulating the effluent in the reaction tank body;
An air supply unit for supplying / regulating the low concentration of dissolved oxygen required for the anammox process in the reaction vessel body; And
And a drain pump connected to the membrane for discharging the effluent in the reaction tank body to the outside,
The polyketone used as the material of the membrane is a copolymer comprising repeating units represented by the following chemical formulas (1) and (2), wherein y / x is 0.01 or less, the molecular weight distribution is 2.5 to 3.5, 7.0 dl / g.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
The method according to claim 1,
Wherein the membrane of the polyketone is formed of a hollow fiber membrane or flat membrane having a plurality of micropores.
delete The method according to claim 1,
Wherein the polyketone membrane is made by applying a polyketone doping solution onto a polyethylene terephthalate support.
Transferring the wastewater to a fluid bed membrane anammox reactor by a wastewater transfer pump;
Removing nitrogen in the wastewater by using a microorganism staying in the fluid bed separation membrane Anamox reaction tank;
Removing the particulate matter and dissolved contaminants in the wastewater by using a polyketone membrane immersed in the fluid bed separation membrane Anamox reaction tank;
Supplying air to the fluidized-bed separation membrane anammosis tank using an air supply unit to supply / regulate low-concentration dissolved oxygen; And
And discharging the wastewater from which the pollutants have been removed to the outside through an outflow pump,
The polyketone used as the material of the membrane is a copolymer comprising repeating units represented by the following chemical formulas (1) and (2), wherein y / x is 0.01 or less, the molecular weight distribution is 2.5 to 3.5, 7.0 dl / g. ≪ / RTI >
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)

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