RU2542303C1 - Automated technological line for surface modification of polymer fibrous material by metal oxide nanoparticles - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: automated technological line for surface modification of polymer fibrous material by metal oxide nanoparticles can be applied in production of filtering material, intended for purification of water from organic pollutions. Composition of automated line includes successively placed hydrolysis unit, container-accumulator of polymer fibrous material, SHF unit, unit of ultrasonic washing and unit for drying modified polymer fibrous material. Travel of polymer fibrous material is carried out by means of tape drive mechanism. Tape drive mechanism consists of pinch rollers, placed on input and output of all units, and guide rollers, placed inside each unit. Container-accumulator is intended for synchronisation of travel speed of polymer fibrous material from reservoir with metal salt solution of hydrolysis unit into SHF unit. Magnetrons in SHF unit are placed parallel to the line of polymer fibrous material travel and are installed with possibility of ensuring alteration in half-wave of maximums and minimums of electromagnetic field. Quarter-wave absorbing traps are placed on input and output of SHF unit. Unit of ultrasonic washing includes reservoir from stainless steel for washing liquid and electronic ultrasonic generator, connected with integrated into reservoir body ultrasonic transformer. Unit for drying of modified polymer fibrous material is made in form of hermetic container, inside of which infra-red lamps are placed in rows, and is equipped with exhaust fan. Work of automated technological line is realised from unit of automated control.

EFFECT: invention makes it possible to provide coordination of work of all units, continuity of process of obtaining filtering material and ensure uniform distribution of metal oxide nanopartilces on the surface of polymer fibrous material.

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Description

The invention relates to technological equipment for the production of filter materials, and more specifically to the production of modified metal oxide nanoparticles of polymeric fibrous material (PVM) with photocatalytic activity, which can be used in filters for water purification from pollution of organic origin, including bacteriological.

The prior art system for modifying objects with nanoparticles according to patent RU 2212268, IPC B01D 39/08, B82B 1/00, B29C 71/04, publ. 09/20/2003. The system is designed to obtain filter elements by modifying various materials with metal nanoparticles and contains a reactor with a solution of a modifying substance in which the objects to be modified are placed, an ionizing gamma radiation source located at the same level with the specified reactor and placed with it in a room with biological radiation protection , thus forming a modification block. In addition, the system is additionally equipped with an inert gas cylinder, a solvent flushing unit, a tank with a mixing device for mixing a solution of a surfactant in a non-polar solvent with an aqueous solution of metal salts, connected by corresponding highways equipped with taps, with the upper part of the said reactor. The solvent washing unit of the reactor is formed by tanks located above the reactor with liquid hydrocarbons, a water-alcohol mixture and distilled water, equipped in the lower parts with drain pipes with taps connected to the line connected with the upper part of the reactor. At the bottom of the reactor there is an outlet pipe connected through a line equipped with a booster pump through an absorber of metal nanoparticles remaining in the solution to the solvent regeneration unit. The solvent recovery unit consists of distillation columns designed for hydrocarbon recovery, water-alcohol mixture, distillation and water purification. The outlet fittings of the distillation columns are connected via a line equipped with taps and a booster pump to the inlet fittings of the capacities of the reactor washing unit.

The system according to patent RU 2212268 due to the reuse of solvents and flushing agents and the possibility of re-adsorption of nanoparticles from a fresh portion of the modifying solution has increased efficiency and economy.

The disadvantage of this system is the complexity of the process and the equipment used, as well as the increased danger of work (source of ionizing gamma radiation, balloon economy, organic solvents). In addition, the use of such a system does not allow to modify the surface of polymeric materials, since the objects modified in it are processed with organic solvents.

The closest adopted for the prototype is a system for modifying polymeric fibrous materials to implement the method for producing filter material according to the invention patent No. 2401153, IPC B01D 39/16, B82B 3/00, publ. 10.10.2010, intended to obtain filter material by modifying tin dioxide PVM nanoparticles obtained by melt blowing of a polymer from the range of polypropylene, polycarbonate or polyethylene terephthalate. The prototype system comprises a container for an aqueous solution of tin (II) chloride (hydrolysis unit) and a microwave oven for decomposing tin hydroxide and fixing tin dioxide nanoparticles to the FDA (microwave unit). In contrast to the system discussed above in patent RU 2212268, this system is environmentally friendly and more economical, since it allows to obtain and simultaneously fix metal oxide nanoparticles with minimal time and energy costs. Its disadvantage is the large proportion of manual labor when modifying the FDA and, therefore, the high complexity in the manufacture of its large volume and area quantities. Such a system does not ensure the coordination of operations for the production of filter materials from FDA.

The objective of the present invention is to provide a safe, efficient and easy-to-use automated production line for the surface-modified metal oxide nanoparticle filter PVM.

The technical result in solving the problem is to ensure the continuity of the process of obtaining filter material, the consistency of the operation of all blocks, regulation of the speed of movement of the FDA and the uniform distribution of nanoparticles on the surface of the FDA. This ultimately ensures the quality of the resulting filter material and its mass production for use in filters for purifying water from organic pollutants, including bacteriological ones.

The task and the technical result are achieved as follows.

Like the prototype, the inventive automated production line for surface modification of metal oxide PVM nanoparticles contains a hydrolysis unit including a container for a metal salt solution, and a microwave unit for forming and fixing metal oxide nanoparticles on the surface of the PVM.

In contrast to the prototype, the automated line contains additional units: an ultrasonic washing unit of a modified PVM, a drying unit of a modified PVM, and a sealed PMV storage container. The modified PVM ultrasonic washing unit includes a stainless steel tank for washing liquid and an electronic ultrasonic generator connected to an ultrasonic transducer integrated into the tank body. The drying unit of the modified FDA is equipped with an exhaust fan and is made in the form of a sealed container, inside which infrared lamps are installed in rows. The difference from the prototype is also that the automated production line additionally contains a tape drive for moving FDA through successively installed hydrolysis unit, FDA storage container, microwave unit, ultrasonic washing unit of modified FDA and drying unit of modified FDA. The tape drive mechanism is made of pressure rollers installed at the inlet and outlet of the sealed housing of each of these blocks, and guide rollers located inside the sealed housing of each block. The guide rollers inside the FDA storage container are staggered. Inside the ultrasonic washing unit of the modified FDA, the guide rollers are also staggered, for example in pairs. In the drying unit, guide rollers located, for example, in pairs, are installed with the possibility of enveloping the FDA of the rows of infrared lamps. In addition, the magnetrons of the microwave unit are installed parallel to the FDA moving line and with the possibility of alternating maxima and minima of the electromagnetic field with a half-wave frequency, and quarter-wave absorbing traps are installed at the input and output of the microwave unit. An automated production line, in contrast to the prototype, further comprises an automatic control unit. One of the pressure rollers of each block of the automated line, a magnetron power source of the microwave unit, an ultrasonic generator of the ultrasonic washing unit, an exhaust fan, and infrared lamps of the drying unit are connected to the automatic control unit by means of adjustable electric drives.

The sources of information not found devices that are characterized by the same set of essential features as the claimed automated production line. This confirms the novelty of the invention.

Consistently installed and interconnected container-drive and blocks allow you to control the speed of FDA through the automatic control unit and provide a coordinated and continuous process for obtaining filter material with a uniform distribution of nanoparticles on its surface. The location of the guide rollers in the hydrolysis unit and the ultrasonic washing unit, the envelope on both sides of the FDA of infrared lamps ensure a uniform distribution of nanoparticles on its surface, and the location of the magnetrons of the microwave unit at a half-wave distance - uniform fixing of the nanoparticles on the FDA surface. All this, ultimately, improves the quality of the filter material in comparison with the prototype.

The applicant is not aware of such an automated line for surface modification of PVM metal oxide nanoparticles, which, along with the content of the hydrolysis unit, in which hydrolysis of metal salts from their solutions and the formation of metal hydroxides, and the microwave unit, in which metal oxide nanoparticles are formed from microwave hydroxide particles during microwave heating metal and fixed on the FDA, additionally contains an automatic control unit connected to the tape drive through an adjustable power water, a storage container with guide rollers located between the hydrolysis unit and the microwave unit. Also known from the prior art are devices for modifying metal oxide PVM nanoparticles in which magnetrons would be located at half wavelengths to attach nanoparticles to the surface of the PVM. This arrangement of magnetrons ensures uniformity of the electromagnetic field, which, in turn, ensures uniform fixation of nanoparticles on the surface of the FDA and improves the quality of the resulting filter material in comparison with the prototype.

Thus, the claimed solution meets the criterion of "inventive step".

Figure 1 schematically shows an automated production line for surface modification of metal oxide PVM nanoparticles. Figure 2, 3 presents the protocols of bacteriological tests of PVM, the surface of which is modified with titanium dioxide nanoparticles on the inventive automated production line.

An automated production line includes sequentially installed blocks: hydrolysis unit 1, in which hydrolysis of metal salts from their solutions and the formation of metal hydroxides takes place; a microwave unit 2, in which metal oxide nanoparticles are formed during microwave heating from particles of metal hydroxides; ultrasonic washing unit 3 of FDA from loose particles and their agglomerates; a drying unit 4 of a PVM modified with nanoparticles after washing; storage container 5; automatic control unit 6 and a tape drive mechanism consisting of pressure and guide rollers.

The hydrolysis unit 1 is a reservoir 7 made of heat-resistant plastic, in which the pinch rollers 9, 10 of the tape drive are mounted, driven by an adjustable electric drive 8 from the panel of the automatic control unit of the production line 6. The tape drive passing through the block 1 contains, in addition to the pressurized input 9 and pinch output 10 rollers, guide rollers 11. The required FDA speed in the block is set by an adjustable electric drive 8.

Block 2 (microwave block) is a metal cabinet 12 with slotted input and output equipped with quarter-wave traps that prevent microwave radiation from leaving the working chamber of block 2. The size of the slots is determined by the width of the FDA. The tape drive mechanism passing through the cabinet 12, consists of pressure input 13, pressure output 14 and guide rollers 15. Cabinet 12 is equipped with a camera in which 4 magnetrons 16, 17, 18 and 19 are placed. The tape drive is driven through a speed-adjustable adjustable drive 20, which is turned on from the panel of the automatic control unit 6. The joint operation of blocks 1 and 2 is synchronized by the presence of a storage container 5 with guide rollers 21 staggered from top to bottom and output rollers 22. In the container 5 there is an excess of FDA specified by the automatic control unit 6, which allows you to combine tape drives nisms blocks 1 and 2, operating at different speeds, in a single process line. Such a FDA modification line can operate both in intermittent mode, when measured FDA is packed in containers and fed “in batches” to the input of the production line, and in a continuous one when the FDA is fed directly to the input of the production line from the conveyor of the aerodynamic dispersion unit of the polymer melt. Position 23 in the drawing indicates the FDA tape.

Block 3 (ultrasonic washing unit) is a stainless steel tank 24, in which the rollers of the tape drive mechanism are mounted, driven by an adjustable electric drive 25 from the panel of the automatic control unit of the production line 6. The tape drive mechanism includes pressure input 26, pressure output 27 and guides 28 rollers. The required speed of the FDA in the block is set by an adjustable electric drive 25. The necessary cavitation in the flushing fluid poured into the tank 24 is created by an ultrasonic transducer integrated into the hole in the tank body 24, to which an alternating voltage of the corresponding frequency is supplied from the electronic ultrasonic generator 29. Depending on solvent metal salts as a washing liquid can be used, for example, alcohols or water, for example distilled.

Block 4 (drying unit) is a sealed metal container 30 with infrared lamps 31 and a tape drive located in it, which is driven by an adjustable electric drive 32 and is turned on from the panel of the automatic control unit of the production line 6. The tape drive in block 4 includes pressure input 33 , clamping output 34 and guide rollers 35 located in pairs that are staggered. The infrared lamps 31 are arranged in rows, and the guide rollers 35 are arranged so that the FDA envelopes the rows of infrared lamps 31 on both sides for uniform drying of the FDA modified with metal oxide nanoparticles. The required speed of the FDA is set by the adjustable electric drive 32. A powerful exhaust fan 36 is located on the panel panel of the unit 4, which removes moisture from the working volume of the unit 4.

The technological line for the modification of PVM with metal oxide nanoparticles works as follows. FDA is placed in the blocks and the storage container in such a way that it envelops all the rollers at once. Then, an aqueous solution of a metal salt is poured into the tank of heat-resistant plastic 7 of block 1. Then, an alkali solution is added until the pH of the solution is reached, at which particles of the corresponding metal hydroxide are formed and adsorbed onto the FDA.

On the panel of the automatic control unit of the technological line 6, adjustable electric drives 8, 20, 25, 32 of tape drives are switched on and voltage is supplied to the electrical equipment of all the blocks of the technological line according to a predetermined program. After that, the FDA starts at a predetermined adjustable electric drive 8, 20, 25, 32 to move along the guide rollers 11 in the volume of the reservoir 7. The speed of the FDA is set depending on the selected FDA and is determined by the adsorption of metal hydroxide nanoparticles on the FDA fibers. At the outlet of the reservoir 7, the FDA with the metal hydroxide nanoparticles on the surface passes through the pressure rollers 10, where the excess solution is squeezed back into the reservoir of the hydrolysis unit 1. After that, the FDA with the metal hydroxide nanoparticles on the surface passes through the guide rollers 21 to the intermediate storage container 5, which serves as a synchronizer of the tape drive mechanisms of the hydrolysis unit 1 and the next microwave unit. Through the output rollers 22 of the intermediate storage container 5, the FDA with the metal hydroxide nanoparticles on the surface passes through the slot entrance and input rollers 13 to the microwave unit 2. In the FDA unit 2, at a speed determined by the time of complete decomposition of the metal hydroxide to metal oxide and fixing the formed metal oxide nanoparticles on FDA, passes through the radiation zone of 4 magnetrons 16, 17, 18, 19, where the metal hydroxide decomposes to metal oxide and the formed metal oxide nanoparticles are fixed to the surface PVM and fiber. The configuration of the electromagnetic field in the metal cavity created by the magnetrons of the microwave unit 2 is characterized by the presence of alternating maxima and minima at half-wave intervals for uniform heating of the entire treated area of the wet FDA. Wet polypropylene fibers are heated to the softening temperature of the selected PVM, and metal oxide nanoparticles are “soldered” to the surface of the polymer fibers. As metal oxide nanoparticles, tin dioxide can be used, the production method of which is described in the patent for invention of the Russian Federation No. 2401153, taken as a prototype, and other known photoactive metal oxide nanoparticles obtained from solutions of the corresponding salts by the controlled addition of anions (cations) or hydrolysis titanium dioxide, zinc oxide, tungsten trioxide, iron trioxide, etc.

After leaving the block 2 through the output pinch rollers 14 and the slotted exit of the FDA with metal oxide nanoparticles fixed to the surface, it enters through the inlet rollers 26 into the reservoir 24 of the block 3, filled with a liquid, such as water, for ultrasonic washing of the FDA from loose particles and their agglomerates. The required speed of the FDA movement in the block is set by the adjustable electric drive 25 and is determined by the time of complete washing of the FDA from loose particles and their agglomerates. The necessary cavitation in the liquid poured into the tank 24 is created by an ultrasonic transducer integrated in the hole in the tank body 24, to which an alternating voltage of the corresponding frequency is supplied from the electronic ultrasonic generator 29. Through the output pinch rollers 27, where the excess amount of washing liquid is pressed back to the tank of the washing unit 3, the FDA with fixed nanoparticles on the surface through the input pinch rollers 33 enters the infrared drying unit 4, where, passing through the system of guide rollers 35 of the tape drive, is irradiated with infrared lamps 31, as a result of which the liquid from the FDA is evaporated and removed from the working volume of the unit 4 by the exhaust fan 36. The speed of the tape in the working chamber of the unit 4 is determined by the time required for the FDA to completely dry. Through the output rollers 34 of the FDA unit 4 with metal oxide nanoparticles fixed on the surface of the fibers, it is placed in a receiving storage container (not shown in the drawing) and, upon filling it, is transported to the finished goods warehouse. As FDA, polypropylene fibrous materials (PPVM), polyethylene terephthalate (dacron) fibrous materials, polyamide fibrous materials and other similar materials can be used.

An automated production line for surface modification of FDA with metal oxide nanoparticles can operate both in the intermittent mode described above, when measured FDAs are packed in containers and fed to the input of the automated production line in batches, or in a continuous one when FDA is fed to the input of an automated production line directly from conveyor unit aerodynamic dispersion of the polymer melt.

The work of an automated production line for surface modification of PVMM with metal oxide nanoparticles is also shown in a specific example, in which PPVM is chosen as PVM, and titanium dioxide nanoparticles are used to modify its surface.

PPVM in the form of a tape 23 with a length of 30-50 m, a width of 0.45 m and a thickness of 40 mm is placed in blocks 1, 2, 3, 4 and the storage container 5 so that it immediately bends around all the rollers. Then, an aqueous solution of titanium trichloride is poured into the reservoir of heat-resistant plastic 7 of block 1 and a 25% aqueous solution of ammonium hydroxide is added until the solution reaches pH 7. As a result of hydrolysis, particles of titanium hydroxide appear in the solution. Voltage is applied from the control panel of the automatic control unit 6, and adjustable electric drives 8, 20, 25, 32 of the tape drive mechanism and electrical equipment of all units of the processing line are turned on (magnetron power supply, exhaust fan, infrared lamps, ultrasonic generator). PPVM tape 23 along the guide rollers 11 begins to enter the reservoir 7 of block 1 with a solution containing titanium hydroxide particles. The speed of the tape 23 is set by the adjustable electric drive 8. During the time set by the speed of the tape drive (for example, 1 m / h), titanium hydroxide particles are adsorbed onto the PPVM fibers, and then through the pinch rollers 10 the PPVM tape with titanium hydroxide nanoparticles enters an intermediate container drive 5. From the storage container 5, synchronizing the operation of two different-speed guide rollers 10 and 13 of the tape drive, PPVM tape 23 with titanium hydroxide nanoparticles arrives at slotted microwave input unit 2, in which the magnetrons are arranged issuing total power of 4 kW with an operating frequency of 2.45 GHz. Having entered through the clamping input rollers 13 into the working volume of the microwave oven 2, the PPVM 23 tape with titanium hydride nanoparticles on the surface at a given speed begins to stretch under the magnetron emitters, as a result of which the wet polypropylene fibers warm up to a temperature of 60-80 ° C, at which the PPVM softens and titanium hydroxide decomposes to titanium dioxide, and its nanoparticles are “soldered” to the surface of polypropylene fibers. Then the PPVM 32 tape with titanium dioxide nanoparticles fixed to the fibers is stretched through the exit slit gap between the pressure rollers 14 of the microwave unit 2 and is fed to the input pressure rollers 26 of the PPVM washing unit 3 from the non-fixed titanium dioxide nanoparticles and its agglomerates. The speed of movement of the PPVM in block 3 is set by an adjustable electric drive 25 and is determined by the time of complete washing of the PVM from non-fixed particles and their agglomerates. The necessary cavitation in distilled water poured into the tank 24 is created by an ultrasonic transducer built into the hole in the tank body 24, to which alternating voltage of the corresponding frequency is supplied from the electronic ultrasonic generator 29. Through the output pinch rollers 27, where excess water is extracted back to the tank of the washing unit 3, PPVM with fixed titanium dioxide nanoparticles on the surface through the input pinch rollers 33 enters the infrared drying unit 4, where, passing through the system of guide rollers 35 of the tape drive, it is irradiated with infrared lamps 31, as a result of which the water from the PPVM is evaporated and removed from the working volume of block 4 by an exhaust fan 36. The speed of the tape in the working chamber of block 4 is determined by the time required for the PPVM to completely dry . Through the output rollers 34 of the FDA unit 4, with titanium dioxide nanoparticles fixed on the surface of the fibers, it is placed in a receiving storage container (not shown in the drawing) and, when filled, is transported to the finished goods warehouse.

The obtained surface-modified nanoparticles of titanium dioxide PPVM passed the test for antibacterial activity and showed good results, which is confirmed by the test reports (figure 2, 3).

Claims (1)

An automated production line for surface modification of a polymeric fibrous material with metal oxide nanoparticles, comprising a hydrolysis unit including a container for a metal salt solution, and a microwave unit for forming and fixing metal oxide nanoparticles on the surface of the polymeric fibrous material, characterized in that the automated line further comprises an ultrasonic unit washing a modified polymeric fibrous material, comprising a stainless steel reservoir eyuschey steel for the washing liquid and an electronic ultrasonic generator connected to the reservoir body embedded in the ultrasonic transducer; further comprises a drying unit for a modified polymeric fibrous material, equipped with an exhaust fan and made in the form of a sealed container, inside which are installed infrared lamps in rows; additionally contains a sealed container of storage of polymer fibrous material and a tape drive for moving the polymer fibrous material through a hydrolysis unit, a storage container of polymeric fibrous material, a microwave unit, an ultrasonic washing unit of a modified polymeric fibrous material and a drying unit of a modified polymeric fibrous material, the tape drive mechanism is made of pinch rollers installed at the inlet and outlet the sealed enclosure of each of these blocks, and the guide rollers located inside the sealed enclosure of each block, the guide rollers inside the storage container of the polymer fibrous material being staggered, inside the ultrasonic washing unit of the modified polymer fibrous material, the guide rollers are also staggered , in pairs, in the drying unit, guide rollers located in pairs are installed with the possibility of bending around polymer fibers the true material of the rows of infrared lamps, in addition, the magnetrons of the microwave unit are installed parallel to the line of movement of the polymer fibrous material and with the possibility of alternating maxima and minima of the electromagnetic field with a half-wave frequency, and quarter-wave absorbing traps are installed at the input and output of the microwave unit; in addition, the automated production line further comprises an automatic control unit, to which one of the pressure rollers of each block of the automated line, a magnetron power supply of the microwave unit, an ultrasonic generator of the ultrasonic washing unit, an exhaust fan, and infrared lamps of the drying unit are connected via adjustable electric drives.

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