PREPARATION METHOD OF HIGH-FLOW POLYAMIDE COMPOSITE MEMBRANE
The present invention refers to high flow polyamide composite membrane manufacturing method relates to search, 10 nm to 50 nm is provided in the form of a film having an average diameter of pores forming element coupled polyamide active layer characterized manufacturing method of the acidic polymer membrane for treating waste water are disclosed. Water dissolved low molecular weight organic material, such as metal salts of nano 2 is abnormal can be performed effectively using a stand-alone number. Nanocomposite film reverse osmosis membrane derived from a film, molecular weight of 200 to 1000 in organic, organic metal salt of a high molecular weight and number 2 is abnormal for use primarily off and stand-alone, 5 to 10 times as compared to reverse osmosis membrane permeable amount because, water treatment cost can be saved greatly also...copyright 2001. Nanocomposite film used primarily for applications include water purification system, waste water containing in the dye for recycling, of softened water (wednesdays) (wednesdays), number of industrial water similar as is cited. Use nanocomposite membrane for magnifying the following order should satisfy several conditions. I.e., water permeable, durability, and excellent compression-resistant must, pH excellent durability against oxidative attack on temperature and antibacterial such as chlorine must substrate. On most commercial the films are but a majority of condition is satisfied, we must improve the point be most improve water permeability. The improve water permeability, also of, and therefore the running cost and the like will in many nano-sized composite foil. The first reverse osmosis using dechlorination process after the fibrous 1930's, many studies have been performed sacrificial of semipermeable membrane material. Among commercial was cited liquor is a cellulosic hypertrophy [ching just pushes (Asymetric membrane) and polyamide composite membrane (Composite membrane) are disclosed. Reverse osmosis membrane initially developed cellulose total screen operated that a narrow pH range, that modified at high temperatures, using a higher pressure in the motor driving that are inexpensive to manufacture, and that is rich in microorganisms vulnerable due to recently entered the disadvantages are disclosed as well as a substantially unused. Low permeation current polyamide composite film can be improved, salt water etc. excellent insulation layer attached current number times. Polyamide composite membrane such as amine monomer is used mainly with position m - phenylenediamine is piperidinyl number tank 2000. E.g. J. E. The USP 4,259,183 patent of Cadotte, reacting with position the claw which will be a mezzo the id/IPC method performed in a piperidinyl tree number tank disclosure wherein, based on the disclosure by adding said patent techniques and improved physical properties through techniques other patent document disclosure number to post-over. For example USP 4765897, USP 4812270, USP 4824574 techniques and to inorganic strong acid Rejection enhancer embodiment in post-disclosure, USP 6280853 epoxide material post-processing techniques in a film coating disclosure in the nanometer range. In addition USP 4769148, USP 4859384 morning fair piperazine layer is film number adding cationic wet number flow rise techniques for deriving the disclosure in the nanometer range. However, piperidinyl using modified salt film prepared by the number number number point at the height of the doors has been difficult to back the side seams. Another method to form non-woven poly opinion phone layer formed microporous support, said microporous support m - phenylene diamine layer is immersed in a solution to form a m - phenylenediamine, m - phenylenediamine are coated or immersed in the claw which will be a mezzo the id tree again contacting organic solvent and a triggering signal at a polyamide layer forming method by the claw which will be a mezzo the id been frame number. Said method comprises a nonpolar solution by contacting the solution polarity only very thin polyamide layer to cover the conductive interface characterized. The polyamide polymer film water permeable, durability, although there are compression-resistant by a packet detector, such as when the engine is operated in low pressure spent sulfuric acid used for processing the extracted transmission or salt times number decrease in number not been point at the door. , the present invention victims of the polymer membrane in the form of acidic media polyethyleneimine (PEI) and a triggering element coupled to obtain film may be a mesoporous chloride (TMC) by an active layer when the trying to polymerized polyamide, as a result nanofiltration membranes or reverse osmosis membrane field number times required for maintaining the existing rate level is lower than the retardant salt even transmission flow to improve driving pressure and transmits the data to, the arrears of work the present invention. The purpose of the invention is in the field of reverse osmosis membrane nanofiltration membranes or number rate while requiring low driving pressure with improved permeability even under acidic salt times meet manufacturing method of a polymer membrane for treating waste water [...] number are disclosed. Said manufacturing method of the present invention another object is to provide a high pressure liquid coolant according to number number [...] acidic polymer membrane for treating waste water are disclosed. In order to achieve said purposes, aspects of the present invention number 1 in the form of a film having an average diameter of 10 nm to 50 nm pores porous support is immersed in solution polyfunctional amine-containing number 1, number 1 solution layer step number 1 element coupled polyfunctional amine-containing; said number 1 and number 2 solution containing polyfunctional acyl halide solution and a porous support layer is formed by immersing said polyfunctional acyl halide solution layer containing polyfunctional amine-containing number 1 number 2 solution are contacted polyamide active layer forming step number 2; and, Said polyfunctional amine is the number average molecular weight of 60,000 to 200,000 polyethyleneimine in a manufacturing method for treating waste water to prevent the number of acidic polymer membrane [...] substrate. Said polymer membrane is 2,000 ppm concentration of 20% to 90% aqueous sodium chloride salt when the number times 100 psi hereinafter through pressure and rate, the flow rate of 20 to 60 gallon/ft initial transmission2 , Characterized day of 0.1. In hereinafter, the present invention is described therein that are directionally. The polymer membrane of the present invention support of pore sizes and polyfunctional amine formed on said support substrate is 20 to low pressure by even among the polyethyleneimine number average molecular weight of between 60 gallon/ft2 , While maintaining flow transmission of day, 20% to 90% salt times number rate can be achieved simultaneously to effectively deal with acidic waste water including salt can be characterized. Characterized polymer membrane of the present invention is an acidic polymer membrane for treating waste water. Said positive number acidic wastewater petroleum factory, in which factory organic synthesis such as mass, including high concentrations of inorganic the lung it buys wastewater, like in metal cleaning waste water, hydrochloric acid, sulfuric acid, phosphoric acid, fluoric acid, including nitric acid or the like may be disclosed. Spent low pressure driven pressure conditions unlike acidic waste water should advantage of the existing water treatment scheme. 10 Nm to 50 nm in average diameter said porous support process for the porous film is preferred. Having an average diameter of 10 nm has not less than projector flow can be, greater than 50 nm thereof can lower the durability of the membrane. The present invention refers to a porous support constituting said polymer membrane is heated so as to have low pressure by 20 to 60 gallon/ft even porosity2 , While maintaining flow transmission of day, 20% to 90% number rate causes salt times can be achieved simultaneously. Said porous support include, nonwoven fabric coating layer can be in the range of a polymer material, said polymer materials include polysulfone, polyethersulfone, polyimide, polyethylene, polypropylene, polyamide, polyetherimide, polyacrylonitrile, polyvinylidene polymethylmethacrylate polymer consisting flora but the whole of selected from the group consisting 1, one must number them are not disclosed. In particular poly opinion phone preferably is among other things. Said polyfunctional amine-containing number 1 solution be polyfunctional amine it will include water and a polar solution. I.e., said solution includes a multifunctional amine-containing aqueous solution be a polyfunctional amine-containing number 1. Said polyfunctional amine-containing number 1 the concentration of the polyfunctional amine solution 0. 01 To 5% by weight preferably disclosed. Said polyfunctional amine polyfunctional amine compounds used in water bath layer number if not one but specially number, a number average molecular weight of 60,000 to 200,000 polyethyleneimine in preferably. A number average molecular weight less than 2,000 ppm concentration of sodium chloride aqueous solution when 60,000 at the passage of the pressure 100 psi hereinafter, 20% to 90% and initial salt times number rate, initial transmission flow rate of 20 to 60 gallon/ft2 , Wherein the polymeric membrane day number could not be high pressure liquid coolant. Be a linear or branched polyethyleneimine said. Preferably designed as, said number 1 step number 1 30 seconds to 5 minutes and a porous support polyfunctional amine-containing solution by dipping solution layer on the porous support can be polyfunctional containing number 1. The other according to specification in the embodiment, said number 1 step excess amine-containing aqueous solution additionally contains the needed number can be a stand-alone. Excess amine-containing aqueous solution in the presence of amine-containing aqueous solution on said porous support can be due to non-uniform distribution, as a result after serving as the active layer can be formed by polyamide at a non-uniform. The, said aqueous solution of excess aqueous solution onto the support layer is formed from silicon number preferably. Said calling number excess aqueous solution but one particularly number 802.11a packets, for example, sponge, air knife, nitrogen gas blowing, air drying, or the like can be performed by using the compression rolls. The present invention refers to said number 1 solution containing polyfunctional acyl halide and a porous support layer is formed by immersing said polyfunctional acyl halide solution layer number 2 solution containing polyfunctional amine-containing number 1 number 2 number 2 the polyamide solution are contacted an active layer comprising the following steps. Said said polyfunctional acyl halide (acyl halide) polyfunctional acyl halide compound with organic solvents containing solution comprises a nonpolar solution number 2 can be. Said polyfunctional acyl halide for example 2 to 3 of carboxylic acid halide with an aromatic compound, the claw which will be a mezzo the id tree (trimesoyl chloride), at least one selected from the group consisting compounds isocyanate moieties and the [phu the claw which rises with the mask with the claw which rises with the id be a 1. Said organic solvent is a hydrocarbon solvent as the nonpolar solvent can be 6 to 13 carbon polymethylene. For example hexane (Hexane), heptane (Hepthane), octane (octane), nonane (nonane), orl (decane), undecane (undecane), 6 to 13 carbon atoms of boron atoms car (dodecane) and mixed material selected from the group consisting of alkanes using at least one of isocyanate groups isoparaffinic solvent can be 1. Preferably, isopar C, isopar G, isopar E (Exxon), but (Exxon) (SK Chem) or ISOL provided G ISOL provided C used, the one number are not disclosed. Said polyamide active layer formation, while compound and at least one acyl halide compound are reacted are formed from polymerized polyamide produced by porous support is formed on the substrate while adsorbed process are disclosed. The thickness of thin film and a porous support of void in the metal tube preferably remains open to control. Preferably designed as, said number 2 step polyfunctional acyl halide solution polyfunctional amine-containing number 1 number 2 and a porous support layer is formed 30 seconds to 5 minutes in a solution containing an active layer by dipping the polyamide can. In the embodiment of the present invention in one, said number 2 to about 30 minutes in a 5 to 90 °C 40 °C after drying can be. Said polymer membrane is 2,000 ppm concentration of 20% to 90% aqueous sodium chloride salt when the number times 100 psi hereinafter through pressure and rate, initial transmission flow rate 10 to 60 gallon/ft2 , Implementation being day. The, said polymer membrane is acidic wastewater which is operable under a low pressure can be suitable for the treatment. In the embodiment of the present invention is other, said number 1 and number 2 or more times to step 2 sequentially and repetitively, a polymer membrane element coupled 2 at least one layer of polyamide serving as the active layer can be a number a number [...] bath method. In one aspect of the present invention number 2 and number along aspect of the present invention number 1 tank, having an average diameter of 10 nm to 50 nm in the form of a polymer film having pores having the active layer polyamide membrane element coupled therewith, said polymer membrane is 2,000 ppm concentration of 20% to 90% aqueous sodium chloride salt when the number times 100 psi hereinafter through pressure and rate, the flow rate of 20 to 60 gallon/ft initial transmission2 , Day acidic for treating waste water polymer membrane having an number [...] substrate. According to the present invention in the field of reverse osmosis membrane nanofiltration membranes or even low pressure required salt times number rate high transmission flow work efficiency while having polyamide composite layer can be [...] number. According to the present invention implement low pressure membrane number inherent in high pressure liquid coolant amount per unit time by the processing capacity of the second container is filled with water can be mirror number advantageous efficiency of 2000. According to the present invention in the field of reverse osmosis membrane nanofiltration membranes or even under low pressure high pressure liquid coolant number membrane salt times required number rate high transmission flow performance while having acidic dye or acid resistant can be used suitably as a membrane for treating waste water. Hereinafter, preferred embodiment of the present invention to aid in understanding a number etched. In the embodiment of the present invention is to more easily understand for however number being ball only, in the embodiment of the present invention content is restricted by are not correct. A polymer membrane was number such as standard high pressure liquid coolant to table 1. <In the embodiment 1> Cast onto a non-woven fabric material and has a weight of 30 nm is detected polyethyleneimine (molecular weight 60,000) 2 minutes in an aqueous solution in 2% polysulfone support after immersing a number after excess of amine solution present on the surface of a stand-alone, 0. 1 Weight % solution in 1 minutes 10 minutes 60 °C tree the claw which will be a mezzo the id (solvent I sol-a C) immersing a porous polysulfone support in drying the polyamide coated with a layer number was high pressure liquid coolant. <In the embodiment 2> Polyethyleneimine (molecular weight 60,000) 0. 3% By weight and a number in the range of 0.1 weight % and piperazine 2 [...] the same method in the embodiment 1 was high pressure liquid coolant to polyamide composite layer number. <In the embodiment 3> Polyethyleneimine (molecular weight 60,000) 0. 5% By weight and a number in the range of 0.1 weight % and piperazine 2 [...] the same method in the embodiment 1 was high pressure liquid coolant to polyamide composite layer number. <In the embodiment 4> 2 Weight % polyethyleneimine (molecular weight 60,000) and piperazine 0. 3 A number in the range of 0.1% by weight and the high pressure liquid coolant in the embodiment 1 was performed the same method a polyamide [...] number. <In the embodiment 5> 2 Weight % polyethyleneimine (molecular weight 60,000) and piperazine 0. 5% By weight of the polyamide composite layer to a number in the range of 0.1 in the embodiment 1 and the same method [...] number was high pressure liquid coolant. <In the embodiment 6> 2 Weight % polyethyleneimine (60,000 molecular weight) in the range of 0.1% by weight and a number and piperazine 1 the same method in the embodiment 1 was performed a polyamide number [...] high pressure liquid coolant. <Comparison example 1> A number in the range of 0.1 weight % polyethyleneimine (molecular weight 1,800) 2 in the embodiment 1 and the same method performed a polyamide [...] number was high pressure liquid coolant. <Comparison example 2> A polyethyleneimine (molecular weight 25,000) method in the embodiment 1 and the same number in the range of 0.1 to 2% by weight polyamide composite layer number [...] his high pressure liquid coolant. <Comparison example 3> The number in the embodiment 1 and a weight in the range of 0.1% polyethyleneimine instead of piperazine 2 [...] same method was high pressure liquid coolant to polyamide composite layer number. Comparison example 4<> 2 Weight % polyethyleneimine (molecular weight 1,800) and tri the claw which will be a mezzo the id 0. 2 A number in the range of 0.1% by weight and the high pressure liquid coolant in the embodiment 1 was performed the same method a polyamide [...] number. <Comparison example 5> 2 Weight % polyethyleneimine (molecular weight 1,800) and tri the claw which will be a mezzo the id 0. 3 A number in the range of 0.1% by weight and the high pressure liquid coolant in the embodiment 1 was performed the same method a polyamide [...] number. Example experiment 1><: polyamide composite film performance evaluation Said in the embodiment 1 to 6 and comparison example 1 to 5 in number 20 °C in sodium chloride (NaCl) to hold a polyamide composite prepared by the temperature and pressure conditions with an aqueous solution concentration of 2,000 ppm 75psi 2,000 ppm magnesium sulfate (MgSO4 ) Transmission flow rate and salt aqueous solution when the number times measuring rate using, for table 2 have shown to result. As in said table 1, in the case of the flow rate of a 20 gallon/ft in the embodiment 6 in the embodiment 1 to the molecular weight of the polyethyleneimine using 60000 in transmission2 , While the day or more, in the case of example 1 compared to comparison example 5 transmission flow rate 15 gallon/ft2 , Day hereinafter can be know about. <In the embodiment 7>: 2 number bath during coating polyamide composite film Polyethyleneimine (molecular weight 1,800) 1. 4 Weight % polyethyleneimine (molecular weight 60,000) and 0. 6% By weight using the same method in the embodiment 1 of the polyamide having a coated polyamide composite layer number 2 was high pressure liquid coolant. The same method number times said experiment example 1 measured rate transmitted flow and salts, transmission flow rate is NaCl transmission flow rate is 23 gallon/ft2 , Day and, 78% NaCl times number ratio and, MgSO4 Transmission flow rate is 23 gallon/ft2 , Day and, MgSO4 Times ratio number 90. Was 0%. <In the embodiment 8> 1 Weight % polyethyleneimine (molecular weight 60,000) 1 weight % polyethyleneimine (molecular weight 1,800) using the same method in the embodiment 1 and 2 the number of polyamide having a coated polyamide composite film was high pressure liquid coolant. The same method number times said experiment example 1 measured rate transmitted flow and salts, transmission flow rate is NaCl transmission flow rate is 8 gallon/ft2 , Day and, 36% NaCl times number ratio and, MgSO4 Transmission flow rate is 8 gallon/ft2 , Day and, MgSO4 45 Ratio number times. Was 1%. <In the embodiment 9> Polyethyleneimine (molecular weight 1,800) 0. 6 Weight % polyethyleneimine (molecular weight 60,000) and 1. 4% By weight using the same method in the embodiment 1 of the polyamide having a coated polyamide composite layer number 2 was high pressure liquid coolant. The same method number times said experiment example 1 measured rate transmitted flow and salts, transmission flow rate is NaCl transmission flow rate is 13 gallon/ft2 , Day and, 73% NaCl times number ratio and, MgSO4 Transmission flow rate is 13 gallon/ft2 , Day and, MgSO4 Times number ratio 86. Was 0%. Example 2><experiment: polyamide composite film characteristics measuring acid resistant evaluation The present invention according to polyamide composite film acid resistant period is in the range, in the embodiment 1 to in the embodiment 6, and comparison example 1 to 15% by weight in comparison example 5 number prepared by the polyamide composite layer sulfuric acid (H2 SO4 , Sigma non-Aldrich) were measured rate of immersing a revoked salt times the number 25. To this end 20 °C in temperature and pressure conditions 75psi 2,000 ppm concentration of magnesium sulfate (MgSO4 ) Aqueous solution the VIP. MgSO4 Number rate measurement result shown for table 3 back to. In said table 2 as in the embodiment 1 to in the embodiment 6, and comparison example 1 to example 5 was compared in the case of rotary both good. The present invention relates to a preparation method of a polymer membrane for treating acidic wastewater, which comprises: a first step of immersing a film-shaped porous support having pores of average diameter of 10-50 nm in a first solution containing a multifunctional amine to form a first solution layer containing a multifunctional amine on the porous support; and a second step of immersing the porous support having the first solution layer formed thereon in a second solution containing a multifunctional acyl halide, thereby bringing the second solution containing a multifunctional acyl halide in contact with the first solution layer containing a multifunctional amine to form a polyamide active layer, wherein the multifunctional amine is polyethyleneimine having a number average molecular weight of 60,000-200,000. The membrane prepared according to the present invention has a salt rejection required in the fields of nanofiltration membrane or reverse osmosis membrane, even under low pressure, while exhibiting high permeate flux performance and acid resistance, and thus may be preferably used as a membrane for treating acidic wastewater. COPYRIGHT KIPO 2017 In the form of a film having an average diameter of 10 nm to 50 nm pores porous support is immersed in solution polyfunctional amine-containing number 1, number 1 solution layer step number 1 element coupled polyfunctional amine-containing; said number 1 and number 2 solution containing polyfunctional acyl halide solution and a porous support layer is formed by immersing said polyfunctional acyl halide solution layer containing polyfunctional amine-containing number 1 number 2 solution are contacted polyamide active layer forming step number 2; and, said polyfunctional amine is the number average molecular weight of 60,000 to 200,000 is a manufacturing method of polyethyleneimine in acidic polymer membrane for treating waste water. According to Claim 1, said porous support, nonwoven fabric and in the coating layer of a polymer material, said polymer material is polysulfone, polyethersulfone, polyimide, polyethylene, polypropylene, polyamide, polyetherimide, polyacrylonitrile, polymethylmethacrylate polymer consisting manufacturing method wherein the substrate is selected from the group consisting 1 determined as a polyvinylidene flora. According to Claim 1, wherein said polyfunctional amine-containing polyfunctional amine manufacturing method including number 1 solution is water. According to Claim 1, said polyfunctional amine-containing number 1 the concentration of the polyfunctional amine solution 0. 01 To 5% by weight in a non-manufacturing method. According to Claim 1, said number 1 step 30 seconds to 5 minutes and a porous support polyfunctional amine-containing number 1 solution immersing a manufacturing method. According to Claim 1, said polyfunctional acyl halide (acyl halide) number 2 solution comprises a nonpolar solution containing polyfunctional acyl halide compound with organic solvents including their manufacturing method. According to Claim 1, said polyfunctional acyl halide tree the claw which will be a mezzo the id, isocyanate moieties and the [phu the claw which rises with the mask manufacturing method is not less than 1 species selected from the group consisting compounds with the claw which rises with the id. According to Claim 1, said number 2 step polyfunctional acyl halide solution polyfunctional amine-containing number 1 number 2 and a porous support layer is formed 30 seconds to 5 minutes a solution containing immersing manufacturing method. According to Claim 1, in the range from 5 to 30 minutes after said number 2 90 °C 40 °C drying will further including manufacturing method. According to Claim 1, said polymer membrane is an aqueous sodium chloride concentration of 2,000 ppm at the passage of the pressure 100 psi hereinafter, 20% to 90% and initial salt times number rate, initial transmission flow rate of 20 to 60 gallon/ft2 , Manufacturing method characterized in a day. Number 1 to number 10 and number according either anti anti anti tank, having an average diameter of 10 nm to 50 nm in the form of a film on a support polyamide active layer pores porous acidic polymer membrane for treating waste water. According to Claim 11, said polymer membrane is an aqueous sodium chloride concentration of 2,000 ppm at the passage of the pressure 100 psi hereinafter, 20% to 90% and initial salt times number rate, initial transmission flow rate of 20 to 60 gallon/ft2 , Day one having an acidic polymer membrane for treating waste water.