US20150165340A1 - Purification System Comprising Continuous Reactor and Purification Method Using Continuous Reactor - Google Patents

Purification System Comprising Continuous Reactor and Purification Method Using Continuous Reactor Download PDF

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US20150165340A1
US20150165340A1 US14/123,764 US201314123764A US2015165340A1 US 20150165340 A1 US20150165340 A1 US 20150165340A1 US 201314123764 A US201314123764 A US 201314123764A US 2015165340 A1 US2015165340 A1 US 2015165340A1
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Prior art keywords
solution
storage tank
tryptophan
heating medium
temperature
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US14/123,764
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Jong Pal Hong
Chil Won Lee
Hee Wan Lee
Gyeong Rye Choi
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Laminar Co Ltd
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Laminar Co Ltd
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Priority claimed from KR1020120097027A external-priority patent/KR101427324B1/en
Priority claimed from KR1020120107996A external-priority patent/KR101372811B1/en
Application filed by Laminar Co Ltd filed Critical Laminar Co Ltd
Publication of US20150165340A1 publication Critical patent/US20150165340A1/en
Abandoned legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D36/00Filter circuits or combinations of filters with other separating devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/005Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
    • B01D9/0054Use of anti-solvent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/0063Control or regulation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/0081Use of vibrations, e.g. ultrasound
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • B01J19/0013Controlling the temperature of the process
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18Stationary reactors having moving elements inside
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04Indoles; Hydrogenated indoles
    • C07D209/10Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C07D209/16Tryptamines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04Indoles; Hydrogenated indoles
    • C07D209/10Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/20Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D2009/0086Processes or apparatus therefor
    • B01D2009/009Separation of organic compounds by selective or extractive crystallisation with the aid of auxiliary substances forming complex or molecular compounds, e.g. with ureum, thioureum or metal salts
    • B01D2009/0095Separation of organic compounds by selective or extractive crystallisation with the aid of auxiliary substances forming complex or molecular compounds, e.g. with ureum, thioureum or metal salts with the aid of other complex forming substances than ureum, thioureum or metal salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00027Process aspects
    • B01J2219/00033Continuous processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094Jackets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor

Definitions

  • the present invention relates to a purification system comprising a continuous reactor. More particularly, the present invention relates to a purification system configured such that a solution stored in a solution storage tank is dispersed/stirred ultrasonically and sent by an air compressor to a reactor in which the sent solution and a solvent introduced through another pathway are stirred to produce a reaction product, and a purification method using the purification system.
  • organic materials need to be purified.
  • organic materials that are used for organic light-emitting devices are pure target components separated from synthesized materials and are used for thin film deposition. With improvement in technology for purifying organic materials, the luminous efficiency of organic light-emitting devices is improved and the life span is also extended.
  • Tryptophan is an essential amino acid.
  • Conventional technologies for purification of tryptophan include methods disclosed in Japanese Patent Laid-Open Publication Nos. 1983-895, 1984-39857 and 1986-126070.
  • Japanese Patent Laid-Open Publication No. 1986-126070 has a problem in that, particularly when a reaction solution, prepared by a fermentation process and containing large amounts of impurities, is heated at a temperature of 95 ⁇ 100° C. in the presence of activated carbon, the amount of a degraded and colored substance increases because tryptophan contains an unstable indole ring in its structure.
  • It is an object of the present invention to provide an ultrahigh-purity purification system comprising a continuous reactor and configured such that a solution stored in a solution storage tank is dispersed/stirred ultrasonically and sent through an air compressor to a reactor in which the sent solution and a solvent introduced through another pathway are stirred to produce a reaction product and such that an organic material for use in organic light-emitting devices can be produced with an ultrahigh purity of 99.9% or higher in large amounts.
  • Another object of the present invention is to provide an system for purifying tryptophan, which adopts a method of dissolving tryptophan in an acidic or basic solution and then adding a counter solution thereto to neutralize the pH to thereby precipitate tryptophan, and which uses a continuous reactor to enable continuous production and increase the production rate by at least three times compared to conventional methods and the recovery rate and purity of tryptophan, and also which uses a polymer material as an additive to increase the density of particles so as not to be easily broken.
  • a purification system comprises: a solution storage tank configured to store a solution; an ultrasonic disperser configured to ultrasonically disperse particles contained in the solution in the solution storage tank; a stirrer configured to stir the solution stored in the solution storage tank; a heating jacket provided outside the solution storage tank and configured to control the internal temperature of the storage tank; an air compressor configured to suck the solution from the solution storage tank and send the sucked solution to a position next thereto; and a reactor configured to be supplied with the solution sent by the air compressor together with a solvent sent through a separate pathway and to stir the supplied solutions at high speed to continuously produce a reaction product having uniform particles.
  • an organic material for use in organic light-emitting devices can be produced with ultrahigh purity in large amounts.
  • an organic material having an ultrahigh purity of 99.9% or higher can be obtained.
  • an organic electroluminescent device When an organic electroluminescent device is fabricated using the organic material having increased purity as described above, the occurrence of dark spots in the device can reduce, the electrical and optical properties of the device can be improved, and the lifespan of the device can be extended.
  • a continuous reactor is used to increase the recovery rate of tryptophan by about 10% compared to that of convention methods, enable continuous production so as to increase the production rate by at least three times, and increase the purity of tryptophan to 99.9% or higher.
  • a polymer material is added to increase the density of particles so as not to be easily broken.
  • FIG. 1 shows the configuration of an ultrahigh-purity purification system according to the present invention.
  • FIG. 2 shows the detailed configuration of a continuous reactor that is included in the purification system of the present invention.
  • FIG. 3 shows the configuration of a cylinder in a continuous reactor that is included in the purification system of the present invention.
  • FIG. 4 shows the configuration of a system for purifying tryptophan according to another embodiment of the present invention.
  • FIG. 5 is a flow chart showing a method for purifying tryptophan according to the present invention.
  • FIGS. 6 to 8 are photographs showing the change in crystals as a function of the injection rate of sulfuric acid in a method for purifying tryptophan according to the present invention.
  • FIG. 9 shows a particle size distribution as a function of reaction time in a method for purifying tryptophan according to the present invention.
  • FIGS. 10 to 13 are photographs showing the shape of tryptophan crystals as a function of reaction time in a method for purifying tryptophan according to the present invention ( FIG. 10 : 1 hour, FIG. 11 : 6 hours, FIG. 12 : 26 hours, and FIG. 13 : 52 hours).
  • FIG. 14 is a graphic diagram showing the change in particle size as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIG. 15 is a graphic diagram showing the change in recovery rate as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIG. 16 is a graphic diagram showing the change in recovery rate as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIGS. 17 and 18 are photographs showing the change in particle shape as a function of stirring speed in a method for purifying tryptophan according to the present invention ( FIG. 17 : 100 rpm, and FIG. 14 : 300 rpm).
  • FIG. 19 is a graphic diagram showing the change in particle size as a function of stirring speed in a method for purifying tryptophan according to the present invention
  • a purification system comprising a reactor according to the present invention comprises a solution storage tank, an ultrasonic disperser, a stirrer, a heating jacket and an air compressor.
  • the purification system may optionally comprise a filter, a separator, a dewaterer, a dryer or the like.
  • the purification system shown in FIGS. 1 to 3 comprises a reactor.
  • This purification system comprises a solution storage tank 100 , an ultrasonic disperser 200 , an air compressor 300 , a filter cartridge 400 , a temperature controlling unit 500 , a continuous reactor 600 , an organic material separator 700 , an organic material storage chamber 800 and a correction module 900 .
  • the solution storage tank 100 serves to store a solution of an organic material (OLED) in an organic solvent.
  • the concentration of the organic material in the organic solvent is preferably 100 g/L or lower, and if the concentration of the organic material is higher than the upper limit of the above concentration range, a crystallization reaction will be delayed or it will be difficult to obtain the desired purity.
  • organic material refers to any material that is provided between the anode and cathode of an organic electroluminescent device. Examples of an organic material or organometallic material that is used in an organic electroluminescent device include a light-emitting host material and host material, hole injection/transport materials, electron injection/transport materials, and hole/electron blocking layer materials.
  • the heating jacket 110 filled with a heating medium is provided outside the solution storage tank 100 so that the solution in the solution storage tank 100 can be heated up to 350 to dissolve the organic material in the organic solvent.
  • the solution storage tank 100 may further include a stirrer in order to uniformly mix the organic material with the organic solvent.
  • the ultrasonic disperser 200 is included in the solution storage tank 100 and serves to apply ultrasonic waves to the organic material to grind and decompose the organic material to thereby form nanoparticles. Because the organic material is not easily dissolved only by heating, it needs to be forcibly ground in order to increase the efficiency at which it is dissolved.
  • the ultrasonic disperser converts a frequency voltage of 50-60 Hz to high-frequency electrical energy of 20 kHz or higher in an oscillator called a generator, and the high-frequency electrical energy is converted to mechanical vibration by a piezoelectric ceramic material in a converter.
  • This conversion is known as the inverse piezoelectric effect, and the vertical vibration generated thereby is transferred to the liquid sample.
  • expansion negative pressure
  • shrinkage positive pressure
  • the air compressor 300 serves to suck the solution from the solution storage tank 100 and send the sucked solution to the filter cartridge 400 that is a position next thereto. If the temperature of the high-temperature solution is lowered while the solution is sent, the solution is precipitated as crystals, and in order to prevent this phenomenon, the solution should be sent in a pressurized state using the air compressor.
  • a pump may also be used in place of the air compressor, but in this case, crystals can be precipitated as described above, and for this reason, the air compressor is preferably used, as long as a solution to the precipitation problem is not provided.
  • the filter cartridge 400 serves to filter out fine impurities contained in the solution sent by the air compressor 300 and to decolorize the salt or ionic substance produced during the synthesis reaction.
  • the filter cartridge 400 comprises a filter case 410 and a material 420 filled in the filter case 410 , wherein the filled material may consist of one or a mixture of two or more selected from the group consisting of metal oxides, including activated alumina, silica, and titanium oxide, and natural stones, including activated carbon, bentonite, acid clay, and diatomaceous earth.
  • metal oxides including activated alumina, silica, and titanium oxide
  • natural stones including activated carbon, bentonite, acid clay, and diatomaceous earth.
  • the temperature controlling unit 500 serves to increase the temperature of the filter cartridge 400 to prevent crystals from being precipitated in the solution.
  • the temperature controlling unit 500 comprises a casing 510 enclosing the filter cartridge 400 , a heating medium 520 filled in the casing 510 , and a heater 530 for heating the heating medium 520 .
  • the continuous reactor 600 is configured to be supplied with the filtered solution that passed through the filter cartridge 400 together with a semi-solvent stored in a semi-solvent storage tank 10 by a pump P and to stir the supplied solution and semi-solvent to produce a reaction product having uniform particles.
  • the continuous reactor 600 comprises a cylinder 610 , a heating medium-filled chamber 620 , a partitioning plate 630 , a temperature controlling element 640 , a stirring body 650 , a stirring motor 660 , a belt pulley 670 and a belt 671 .
  • the cylinder 610 of the continuous reactor 600 has a reaction chamber 611 that receives the filtered solution and the semi-solvent, and in order to introduce the semi-solvent into the reaction chamber 611 , a semi-solvent injection port 611 a is formed at the upper portion of the cylinder 610 .
  • a solution injection port 611 b for introducing the organic material solution is formed at the lower portion of the cylinder 620 .
  • Reference numeral 611 c indicates a discharge port through which the reaction product is discharged after completion of the reaction.
  • the heating medium-filled chamber 620 is formed along the outer circumference of the reaction chamber 611 in a ring shape and is filled with a heating medium for controlling the temperature of the solution and semi-solvent received in the reaction chamber 611 .
  • the heating medium-filled chamber 620 is divided into a plurality of chambers by a plurality of partitioning plates 630 that are made of a thermal insulating material in order to prevent the heat exchange between the heating media filled in the plurality of heating medium-filled chambers 620 .
  • the temperature gradient of the solution passing through the reaction chamber 611 can be reduced.
  • the temperature gradient can change depending on the temperature of the heating medium.
  • Each of the heating medium-filled chambers 620 may further include a temperature sensor 621 serving to sense the temperature of the heating medium in each of the chambers and transmit the sensed temperature to an analysis and correction module 900 .
  • the temperature controlling element 640 serves to control the temperature of the heating medium and may, for example, be a circulator or a heater.
  • the stirring body 650 has a rod shape, is rotatably provided in the cylinder 610 and serves to stir the solution and semi-solvent received in the cylinder 610 .
  • mixing in the axial direction of the stirring body 650 decreases, and mixing in the radial direction increases.
  • the unstable fluid forms the so-called Taylor vortex in the form of a pair of rings rotating in opposite directions along the direction of the stirring body 650 .
  • This Taylor vortex can be used for fluid stability, because turbulent flow can be created by changing the rotating speed of the stirring body 650 .
  • the stirring motor 660 is disposed below the cylinder 610 and serves to provide a rotating force to the stirring body 650 .
  • the stirring motor 660 may be a speed-changeable stirring motor whose rotating speed can be controlled in the range of 10-2000 rpm by a direct voltage controller (not shown).
  • the rotating speed of the stirring body 650 that is rotated by the stirring motor 660 can also be changed in the above range (10-2000 pm) to cause turbulent flow in the solution.
  • the stirring motor 660 and the stirring body 650 are connected indirectly to each other by the belt pulley 670 and the belt 671 .
  • the stirring body 650 is maintained at a high temperature because the high internal temperature of the cylinder 610 is conducted thereto. Thus, if the high temperature of the stirring body is transferred directly to the stirring motor 660 , the life span of the stirring motor 660 can be shortened. For this reason, the stirring body 650 is connected indirectly to the stirring motor 660 by the belt 671 in order to block heat transfer therebetween.
  • the connection of the stirring body to the stirring motor by the belt has been described by way of example, the connection is not limited by the belt, and the connection can be achieved by a chain or a gear.
  • the wall surface of the reaction chamber 611 and the heating medium-filled chamber 620 may be coated with Teflon 622 in order to provide corrosion resistance to the wall surface.
  • Teflon 622 may also be made of hastelloy-C.
  • Hastelloy-C is an acid-resistant alloy having a very high corrosion resistance, and thus when it is applied to a portion that frequently contacts a chemical solution, such as the cylinder 610 of the present invention, it can provide corrosion resistance.
  • the organic material separator 700 is connected to the discharge port 611 c of the continuous reactor 600 and serves to separate the slurry-type reaction product, discharged from the continuous reactor 600 , into a solid organic material and a liquid.
  • the organic material storage chamber 800 serves to store the solid organic material separated by the organic material separator 700 .
  • the analysis and correction module 900 serves to collect the liquid separated by the organic material separator 700 , and then analyze whether or not the state of the collected liquid is normal and correct the process conditions into optimal process conditions on the basis of the analyzed data.
  • the correction function can be controlled by a computer.
  • the system for purifying tryptophan comprises a filter 10 for filtering solids, a storage tank 20 , a heating tank 30 , an air compressor 40 , a continuous reactor 50 , a dewaterer 60 and a dryer 70 .
  • the filter 10 for filtering solids is configured to filter out solids from a tryptophan solution while allowing the solution to pass through the filter.
  • the filter 10 has a mesh size (or pore size) of 0.1 ⁇ m or larger, and preferably 0.1-0.5 ⁇ m, so that it filters out solids having a size of 0.5 ⁇ m or larger from the tryptophan solution and allows only fine solids having a size of less than 0.5 ⁇ m to pass therethrough.
  • the filter 10 performs a first purification step.
  • the storage tank 20 serves to store the tryptophan solution that passed through the filter 10 .
  • the storage tank 20 includes a temperature sensor 21 so that the temperature of the tryptophan solution stored in the storage tank 20 can be sensed in real time.
  • the heating jacket 30 is provided outside the storage tank and functions to control the internal temperature of the storage tank 20 .
  • the heating jacket 30 is filled with a heating medium and provided in such a manner that a portion of the storage tank 20 is placed in the heating jacket 30 such that the tryptophan solution in the storage tank 20 can be controlled to a suitable temperature by heating the heating medium by a heat source.
  • the air compressor 40 functions to suck the tryptophan solution from the storage tank 20 and send the sucked solution to a position next thereto.
  • a pump may be provided in place of the air compressor.
  • the continuous reactor 50 is configured to be supplied with the tryptophan solution sent by the air compressor 40 together with sulfuric acid sent through a separate pathway and to stir the supplied solutions to continuously produce a reaction product.
  • the continuous reactor is as described above, and thus the detailed description thereof is omitted.
  • the dewaterer 60 is connected to the discharge port of the continuous reactor and functions to separate a liquid from a slurry-type reaction product discharged from the continuous reactor. It may be a centrifugation-type dewaterer.
  • a method for purifying tryptophan according to the present invention is performed in the following order (see FIG. 5 ).
  • Step 1 is a solid removal step (S 10 ).
  • the tryptophan solution is passed through a filter to remove solids having a size larger than a predetermined size, before it is stored in the storage tank.
  • the filter that is used in the solid removal step preferably has a mesh size (or pore size) of 0.1-0.5 ⁇ m.
  • a mesh size or pore size
  • Step 2 is a pH adjusting step (S 20 ).
  • caustic soda NaOH
  • the pH is preferably adjusted to 3-11.
  • Step 3 is a temperature controlling step (S 30 ).
  • the temperature of the tryptophan solution is controlled to a suitable temperature using the heating jacket provided outside the storage tank.
  • Step 4 is a density increasing step (S 40 ).
  • a polymer material is added to the tryptophan solution in the storage tank to increase the density of particles in the tryptophan solution. This step is performed using the continuous reactor.
  • the polymer material may be any one selected from among PVA (polyvinyl alcohol), carrageenan, alginic acid, and gelatin.
  • PVA polyvinyl alcohol
  • carrageenan polyvinyl alcohol
  • alginic acid alginic acid
  • gelatin gelatin
  • the size of crystals increases with the passage of time, and the growth rate of tryptophan crystals is higher than that in the case in which no polymer is added.
  • an acid solution particularly sulfuric acid solution
  • particles in the tryptophan solution grow to a size of about 300 ⁇ m or larger.
  • the particles are easily broken by sonication due to their low strength, but the strength of the particles is increased when a polymer material having a low molecular weight is added thereto.
  • Step 5 is a supply step (S 50 ).
  • the tryptophan solution in the storage tank is continuously supplied to the continuous reactor.
  • the supply of the tryptophan solution can be automatically performed by the air compressor or the like.
  • Step 6 is a crystal precipitation step (S 60 ).
  • an acid solution (particularly sulfuric acid solution) is added to the tryptophan solution introduced into the continuous reactor to neutralize the pH of the tryptophan solution to thereby precipitate crystal particles.
  • the tryptophan solution is an amphoteric substance that easily dissolves in an acidic or basic solution, and thus this tryptophan solution is dissolved in an acidic or basic solution, after which a counter solution is added thereto to neutralize the pH, thereby precipitating crystals.
  • the tryptophan solution is dissolved in a sodium hydroxide solution, and then an acidic solution is added thereto.
  • Step 7 is a solid-liquid separation step (S 70 ).
  • the crystal particles that precipitated in the continuous reactor are dewatered by the dewaterer, thereby separating the crystals into a solid and a liquid.
  • the resulting tryptophan having a high water content is introduced into a centrifugation-type dewaterer, and the dewaterer is operated to reduce the water content to 60% or lower.
  • a suitable dewatering time is determined by performing dewatering for any amount of time, collecting the dewatered tryptophan sludge, measuring the water content of the sludge, and adjusting the dewatering time based on the measurement results.
  • the rotating speed of the dewaterer is 5,000-12,000 rpm, and the dewatering time is 50-60 minutes. If the rotating speed is lower than 500 rpm, the dewatering time will be too long, and if the rotating speed is higher than 12,000 rpm, the dewatering rate will not significantly differ from that in the case in which the rotating speed is lower than 12,000 rpm, and thus the efficiency of dewatering will be reduced.
  • Step 8 is a drying step (S 80 ).
  • the dewatered tryptophan sludge cake still has a high water content, the water content is lowered to 10% or less by hot-air drying to form powder.
  • a process of washing the sludge cake and separating the washing water by centrifugation may further be performed. This powdering process provides high-purity tryptophan.
  • Tryptophan concentration 200 g/L
  • Injection rate of sulfuric acid 0.5 mL/min, 2 mL/min, and injection at a time.
  • FIGS. 6 to 8 are microscopic photographs of 1, 2 and 3 in Table 1 above.
  • Tryptophan concentration 100 g/L
  • Amount and rate of injection of sulfuric acid 100 mL & 16.7 mL/min;
  • the recovery rate was about 95% or higher without significantly changing depending on the reaction time, suggesting that tryptophan precipitated within a short time.
  • Tryptophan concentration 10, 100 and 200 g/L;
  • lowering the dissolution concentration of tryptophan is a method capable of inhibiting nucleation and that the method of the present invention is suitable for lowering nucleation. It is believed that as nucleation decreases, nuclei are attached to dissolved tryptophan to cause crystal growth.
  • Tryptophan concentration 10 g/L
  • the material of this Experiment is a sheet-like material comprising particles having a weak bonding strength therebetween.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Indole Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The present invention relates to a purification system configured such that a solution stored in a solution storage tank is dispersed/stirred ultrasonically and sent by an air compressor to a reactor in which the sent solution and a solvent introduced through another pathway are stirred to produce a reaction product, and a purification method using the purification system.

Description

    TECHNICAL FIELD
  • The present invention relates to a purification system comprising a continuous reactor. More particularly, the present invention relates to a purification system configured such that a solution stored in a solution storage tank is dispersed/stirred ultrasonically and sent by an air compressor to a reactor in which the sent solution and a solvent introduced through another pathway are stirred to produce a reaction product, and a purification method using the purification system.
  • BACKGROUND ART
  • Generally, many materials need to be purified. Similarly, organic materials, as well as essential amino acids that are used in feed additives, medical drugs, health foods and the like, need to be purified. For example, organic materials that are used for organic light-emitting devices are pure target components separated from synthesized materials and are used for thin film deposition. With improvement in technology for purifying organic materials, the luminous efficiency of organic light-emitting devices is improved and the life span is also extended.
  • For the mass production of organic materials, technology for purification of organic materials, which has shortened process time and improved purification efficiency, is necessary.
  • Tryptophan is an essential amino acid. Conventional technologies for purification of tryptophan include methods disclosed in Japanese Patent Laid-Open Publication Nos. 1983-895, 1984-39857 and 1986-126070.
  • However, it was found that the method employing an ultrafiltration membrane as disclosed in Japanese Patent Laid-Open Publication No. 1983-895 could not remove impurities at a fixed removal rate, and thus excessive load was applied to a non-polar highly porous resin to shorten the regenerative cycle of the resin.
  • In addition, in the case of the method disclosed in Japanese Patent Laid-Open Publication No. 1984-39857, the degree of removal of impurity is low and it is difficult to obtain a crystal having a transmission of 95% or higher.
  • Moreover, the method disclosed in Japanese Patent Laid-Open Publication No. 1986-126070 has a problem in that, particularly when a reaction solution, prepared by a fermentation process and containing large amounts of impurities, is heated at a temperature of 95˜100° C. in the presence of activated carbon, the amount of a degraded and colored substance increases because tryptophan contains an unstable indole ring in its structure.
  • DISCLOSURE Technical Problem
  • It is an object of the present invention to provide an ultrahigh-purity purification system comprising a continuous reactor and configured such that a solution stored in a solution storage tank is dispersed/stirred ultrasonically and sent through an air compressor to a reactor in which the sent solution and a solvent introduced through another pathway are stirred to produce a reaction product and such that an organic material for use in organic light-emitting devices can be produced with an ultrahigh purity of 99.9% or higher in large amounts.
  • Another object of the present invention is to provide an system for purifying tryptophan, which adopts a method of dissolving tryptophan in an acidic or basic solution and then adding a counter solution thereto to neutralize the pH to thereby precipitate tryptophan, and which uses a continuous reactor to enable continuous production and increase the production rate by at least three times compared to conventional methods and the recovery rate and purity of tryptophan, and also which uses a polymer material as an additive to increase the density of particles so as not to be easily broken.
  • Technical Solution
  • A purification system according to the present invention comprises: a solution storage tank configured to store a solution; an ultrasonic disperser configured to ultrasonically disperse particles contained in the solution in the solution storage tank; a stirrer configured to stir the solution stored in the solution storage tank; a heating jacket provided outside the solution storage tank and configured to control the internal temperature of the storage tank; an air compressor configured to suck the solution from the solution storage tank and send the sucked solution to a position next thereto; and a reactor configured to be supplied with the solution sent by the air compressor together with a solvent sent through a separate pathway and to stir the supplied solutions at high speed to continuously produce a reaction product having uniform particles.
  • Advantageous Effects
  • According to the configuration of the present invention, an organic material for use in organic light-emitting devices can be produced with ultrahigh purity in large amounts. Particularly, according to a crystallization method of the present invention, an organic material having an ultrahigh purity of 99.9% or higher can be obtained.
  • When an organic electroluminescent device is fabricated using the organic material having increased purity as described above, the occurrence of dark spots in the device can reduce, the electrical and optical properties of the device can be improved, and the lifespan of the device can be extended.
  • Moreover, according to the present invention, a continuous reactor is used to increase the recovery rate of tryptophan by about 10% compared to that of convention methods, enable continuous production so as to increase the production rate by at least three times, and increase the purity of tryptophan to 99.9% or higher.
  • In addition, according to the present invention, a polymer material is added to increase the density of particles so as not to be easily broken.
  • DESCRIPTION OF DRAWINGS
  • FIG. 1 shows the configuration of an ultrahigh-purity purification system according to the present invention.
  • FIG. 2 shows the detailed configuration of a continuous reactor that is included in the purification system of the present invention.
  • FIG. 3 shows the configuration of a cylinder in a continuous reactor that is included in the purification system of the present invention.
  • FIG. 4 shows the configuration of a system for purifying tryptophan according to another embodiment of the present invention.
  • FIG. 5 is a flow chart showing a method for purifying tryptophan according to the present invention.
  • FIGS. 6 to 8 are photographs showing the change in crystals as a function of the injection rate of sulfuric acid in a method for purifying tryptophan according to the present invention.
  • FIG. 9 shows a particle size distribution as a function of reaction time in a method for purifying tryptophan according to the present invention.
  • FIGS. 10 to 13 are photographs showing the shape of tryptophan crystals as a function of reaction time in a method for purifying tryptophan according to the present invention (FIG. 10: 1 hour, FIG. 11: 6 hours, FIG. 12: 26 hours, and FIG. 13: 52 hours).
  • FIG. 14 is a graphic diagram showing the change in particle size as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIG. 15 is a graphic diagram showing the change in recovery rate as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIG. 16 is a graphic diagram showing the change in recovery rate as a function of the dissolution concentration of tryptophan in a method for purifying tryptophan according to the present invention.
  • FIGS. 17 and 18 are photographs showing the change in particle shape as a function of stirring speed in a method for purifying tryptophan according to the present invention (FIG. 17: 100 rpm, and FIG. 14: 300 rpm).
  • FIG. 19 is a graphic diagram showing the change in particle size as a function of stirring speed in a method for purifying tryptophan according to the present invention
  • MODE FOR INVENTION
  • A purification system comprising a reactor according to the present invention comprises a solution storage tank, an ultrasonic disperser, a stirrer, a heating jacket and an air compressor. Depending on the kind of material to be purified, the purification system may optionally comprise a filter, a separator, a dewaterer, a dryer or the like.
  • Embodiment 1
  • The purification system shown in FIGS. 1 to 3 comprises a reactor. This purification system comprises a solution storage tank 100, an ultrasonic disperser 200, an air compressor 300, a filter cartridge 400, a temperature controlling unit 500, a continuous reactor 600, an organic material separator 700, an organic material storage chamber 800 and a correction module 900.
  • The solution storage tank 100 serves to store a solution of an organic material (OLED) in an organic solvent. The concentration of the organic material in the organic solvent is preferably 100 g/L or lower, and if the concentration of the organic material is higher than the upper limit of the above concentration range, a crystallization reaction will be delayed or it will be difficult to obtain the desired purity. As used herein, the term “organic material” refers to any material that is provided between the anode and cathode of an organic electroluminescent device. Examples of an organic material or organometallic material that is used in an organic electroluminescent device include a light-emitting host material and host material, hole injection/transport materials, electron injection/transport materials, and hole/electron blocking layer materials.
  • The heating jacket 110 filled with a heating medium is provided outside the solution storage tank 100 so that the solution in the solution storage tank 100 can be heated up to 350 to dissolve the organic material in the organic solvent.
  • In addition, the solution storage tank 100 may further include a stirrer in order to uniformly mix the organic material with the organic solvent.
  • The ultrasonic disperser 200 is included in the solution storage tank 100 and serves to apply ultrasonic waves to the organic material to grind and decompose the organic material to thereby form nanoparticles. Because the organic material is not easily dissolved only by heating, it needs to be forcibly ground in order to increase the efficiency at which it is dissolved.
  • For reference, the ultrasonic disperser converts a frequency voltage of 50-60 Hz to high-frequency electrical energy of 20 kHz or higher in an oscillator called a generator, and the high-frequency electrical energy is converted to mechanical vibration by a piezoelectric ceramic material in a converter. This conversion is known as the inverse piezoelectric effect, and the vertical vibration generated thereby is transferred to the liquid sample. By at least 20,000 vibrations per second and constant vibrational amplitude of a probe (or tip) through which the ultrasonic vertical vibration is transferred, expansion (negative pressure) and shrinkage (positive pressure) occurs in the sample, and fine bubbles generated in this procedure are intensively broken during amplification of positive pressure. This is known as cavitation, and at this time, high-temperature and high-pressure instantaneous shock waves having a pressure of about 1000 bar and an instantaneous temperature of about 5000 K occur and act as a very high energy source to grind the organic material particles.
  • The air compressor 300 serves to suck the solution from the solution storage tank 100 and send the sucked solution to the filter cartridge 400 that is a position next thereto. If the temperature of the high-temperature solution is lowered while the solution is sent, the solution is precipitated as crystals, and in order to prevent this phenomenon, the solution should be sent in a pressurized state using the air compressor. A pump may also be used in place of the air compressor, but in this case, crystals can be precipitated as described above, and for this reason, the air compressor is preferably used, as long as a solution to the precipitation problem is not provided.
  • The filter cartridge 400 serves to filter out fine impurities contained in the solution sent by the air compressor 300 and to decolorize the salt or ionic substance produced during the synthesis reaction.
  • The filter cartridge 400 comprises a filter case 410 and a material 420 filled in the filter case 410, wherein the filled material may consist of one or a mixture of two or more selected from the group consisting of metal oxides, including activated alumina, silica, and titanium oxide, and natural stones, including activated carbon, bentonite, acid clay, and diatomaceous earth.
  • The temperature controlling unit 500 serves to increase the temperature of the filter cartridge 400 to prevent crystals from being precipitated in the solution. The temperature controlling unit 500 comprises a casing 510 enclosing the filter cartridge 400, a heating medium 520 filled in the casing 510, and a heater 530 for heating the heating medium 520.
  • The continuous reactor 600 is configured to be supplied with the filtered solution that passed through the filter cartridge 400 together with a semi-solvent stored in a semi-solvent storage tank 10 by a pump P and to stir the supplied solution and semi-solvent to produce a reaction product having uniform particles. The continuous reactor 600 comprises a cylinder 610, a heating medium-filled chamber 620, a partitioning plate 630, a temperature controlling element 640, a stirring body 650, a stirring motor 660, a belt pulley 670 and a belt 671.
  • The cylinder 610 of the continuous reactor 600 has a reaction chamber 611 that receives the filtered solution and the semi-solvent, and in order to introduce the semi-solvent into the reaction chamber 611, a semi-solvent injection port 611 a is formed at the upper portion of the cylinder 610. In addition, a solution injection port 611 b for introducing the organic material solution is formed at the lower portion of the cylinder 620.
  • Reference numeral 611 c indicates a discharge port through which the reaction product is discharged after completion of the reaction.
  • The heating medium-filled chamber 620 is formed along the outer circumference of the reaction chamber 611 in a ring shape and is filled with a heating medium for controlling the temperature of the solution and semi-solvent received in the reaction chamber 611.
  • The heating medium-filled chamber 620 is divided into a plurality of chambers by a plurality of partitioning plates 630 that are made of a thermal insulating material in order to prevent the heat exchange between the heating media filled in the plurality of heating medium-filled chambers 620.
  • Thus, when the heating media filled in the heating medium-filled chambers 620 divided by the partitioning plates 630 are heated to different temperatures, the temperature gradient of the solution passing through the reaction chamber 611 can be reduced. The temperature gradient can change depending on the temperature of the heating medium.
  • Each of the heating medium-filled chambers 620 may further include a temperature sensor 621 serving to sense the temperature of the heating medium in each of the chambers and transmit the sensed temperature to an analysis and correction module 900.
  • The temperature controlling element 640 serves to control the temperature of the heating medium and may, for example, be a circulator or a heater.
  • The stirring body 650 has a rod shape, is rotatably provided in the cylinder 610 and serves to stir the solution and semi-solvent received in the cylinder 610. As the stirring body 650 rotates, mixing in the axial direction of the stirring body 650 decreases, and mixing in the radial direction increases. Thus, when a flow in the axial direction of the stirring body 650 exists, mixing between cells occurs, but a fluid close to the stirring body 650 is fixed by the centrifugal force to tend to move toward the inner wall of the cylinder 610. The unstable fluid forms the so-called Taylor vortex in the form of a pair of rings rotating in opposite directions along the direction of the stirring body 650. This Taylor vortex can be used for fluid stability, because turbulent flow can be created by changing the rotating speed of the stirring body 650.
  • The stirring motor 660 is disposed below the cylinder 610 and serves to provide a rotating force to the stirring body 650. The stirring motor 660 may be a speed-changeable stirring motor whose rotating speed can be controlled in the range of 10-2000 rpm by a direct voltage controller (not shown). Thus, the rotating speed of the stirring body 650 that is rotated by the stirring motor 660 can also be changed in the above range (10-2000 pm) to cause turbulent flow in the solution.
  • The stirring motor 660 and the stirring body 650 are connected indirectly to each other by the belt pulley 670 and the belt 671. The stirring body 650 is maintained at a high temperature because the high internal temperature of the cylinder 610 is conducted thereto. Thus, if the high temperature of the stirring body is transferred directly to the stirring motor 660, the life span of the stirring motor 660 can be shortened. For this reason, the stirring body 650 is connected indirectly to the stirring motor 660 by the belt 671 in order to block heat transfer therebetween. Although the connection of the stirring body to the stirring motor by the belt has been described by way of example, the connection is not limited by the belt, and the connection can be achieved by a chain or a gear.
  • Meanwhile, the wall surface of the reaction chamber 611 and the heating medium-filled chamber 620 may be coated with Teflon 622 in order to provide corrosion resistance to the wall surface. Alternatively, it may also be made of hastelloy-C. Hastelloy-C is an acid-resistant alloy having a very high corrosion resistance, and thus when it is applied to a portion that frequently contacts a chemical solution, such as the cylinder 610 of the present invention, it can provide corrosion resistance.
  • The organic material separator 700 is connected to the discharge port 611 c of the continuous reactor 600 and serves to separate the slurry-type reaction product, discharged from the continuous reactor 600, into a solid organic material and a liquid.
  • The organic material storage chamber 800 serves to store the solid organic material separated by the organic material separator 700.
  • The analysis and correction module 900 serves to collect the liquid separated by the organic material separator 700, and then analyze whether or not the state of the collected liquid is normal and correct the process conditions into optimal process conditions on the basis of the analyzed data. The correction function can be controlled by a computer.
  • Embodiment 2
  • Hereinafter, a system for purifying tryptophan will be described which comprises, in addition to the above-described continuous reactor, storage tank, stirrer, disperser and heating jacket, a dewaterer and a dryer.
  • As shown in FIG. 4, the system for purifying tryptophan comprises a filter 10 for filtering solids, a storage tank 20, a heating tank 30, an air compressor 40, a continuous reactor 50, a dewaterer 60 and a dryer 70.
  • The filter 10 for filtering solids is configured to filter out solids from a tryptophan solution while allowing the solution to pass through the filter. Herein, the filter 10 has a mesh size (or pore size) of 0.1 μm or larger, and preferably 0.1-0.5 μm, so that it filters out solids having a size of 0.5 μm or larger from the tryptophan solution and allows only fine solids having a size of less than 0.5 μm to pass therethrough. As a result, the filter 10 performs a first purification step. The storage tank 20 serves to store the tryptophan solution that passed through the filter 10. Herein, the storage tank 20 includes a temperature sensor 21 so that the temperature of the tryptophan solution stored in the storage tank 20 can be sensed in real time.
  • The heating jacket 30 is provided outside the storage tank and functions to control the internal temperature of the storage tank 20. The heating jacket 30 is filled with a heating medium and provided in such a manner that a portion of the storage tank 20 is placed in the heating jacket 30 such that the tryptophan solution in the storage tank 20 can be controlled to a suitable temperature by heating the heating medium by a heat source.
  • The air compressor 40 functions to suck the tryptophan solution from the storage tank 20 and send the sucked solution to a position next thereto. A pump may be provided in place of the air compressor.
  • The continuous reactor 50 is configured to be supplied with the tryptophan solution sent by the air compressor 40 together with sulfuric acid sent through a separate pathway and to stir the supplied solutions to continuously produce a reaction product.
  • The continuous reactor is as described above, and thus the detailed description thereof is omitted.
  • The dewaterer 60 is connected to the discharge port of the continuous reactor and functions to separate a liquid from a slurry-type reaction product discharged from the continuous reactor. It may be a centrifugation-type dewaterer.
  • Embodiment 3
  • A method for purifying tryptophan according to the present invention is performed in the following order (see FIG. 5).
  • Step 1 is a solid removal step (S10).
  • In the solid removal step, the tryptophan solution is passed through a filter to remove solids having a size larger than a predetermined size, before it is stored in the storage tank.
  • The filter that is used in the solid removal step preferably has a mesh size (or pore size) of 0.1-0.5 μm. Thus, dissolved solids having a size of 0.5 μm or larger, contained in the tryptophan solution, are filtered out, and thus the tryptophan solution contains only fine solids having a size smaller than 0.5 μm.
  • Step 2 is a pH adjusting step (S20).
  • In the pH adjusting step, caustic soda (NaOH) is introduced into the storage tank to adjust the pH of the tryptophan solution. Herein, the pH is preferably adjusted to 3-11.
  • Step 3 is a temperature controlling step (S30).
  • In the temperature controlling step, the temperature of the tryptophan solution is controlled to a suitable temperature using the heating jacket provided outside the storage tank.
  • Step 4 is a density increasing step (S40).
  • In the density increasing step, a polymer material is added to the tryptophan solution in the storage tank to increase the density of particles in the tryptophan solution. This step is performed using the continuous reactor.
  • Herein, the polymer material may be any one selected from among PVA (polyvinyl alcohol), carrageenan, alginic acid, and gelatin. As can be seen in FIG. 4, for example, when PVA and gelatin are applied, the size of crystals increases with the passage of time, and the growth rate of tryptophan crystals is higher than that in the case in which no polymer is added. In addition, as the content of an acid solution (particularly sulfuric acid solution) to be described in the following step 6 increases, the size of growing crystals increases.
  • Further, due to addition of the polymer material, particles in the tryptophan solution grow to a size of about 300 μm or larger. In this case, the particles are easily broken by sonication due to their low strength, but the strength of the particles is increased when a polymer material having a low molecular weight is added thereto.
  • Step 5 is a supply step (S50).
  • In the supply step, the tryptophan solution in the storage tank is continuously supplied to the continuous reactor. The supply of the tryptophan solution can be automatically performed by the air compressor or the like.
  • The configuration of the continuous reactor will be described later.
  • Step 6 is a crystal precipitation step (S60).
  • In the crystal precipitation step, an acid solution (particularly sulfuric acid solution) is added to the tryptophan solution introduced into the continuous reactor to neutralize the pH of the tryptophan solution to thereby precipitate crystal particles.
  • In other words, the tryptophan solution is an amphoteric substance that easily dissolves in an acidic or basic solution, and thus this tryptophan solution is dissolved in an acidic or basic solution, after which a counter solution is added thereto to neutralize the pH, thereby precipitating crystals. For example, the tryptophan solution is dissolved in a sodium hydroxide solution, and then an acidic solution is added thereto.
  • Step 7 is a solid-liquid separation step (S70).
  • In the solid-liquid separation step, the crystal particles that precipitated in the continuous reactor are dewatered by the dewaterer, thereby separating the crystals into a solid and a liquid.
  • In other words, the resulting tryptophan having a high water content is introduced into a centrifugation-type dewaterer, and the dewaterer is operated to reduce the water content to 60% or lower. A suitable dewatering time is determined by performing dewatering for any amount of time, collecting the dewatered tryptophan sludge, measuring the water content of the sludge, and adjusting the dewatering time based on the measurement results.
  • In a preferred embodiment, the rotating speed of the dewaterer is 5,000-12,000 rpm, and the dewatering time is 50-60 minutes. If the rotating speed is lower than 500 rpm, the dewatering time will be too long, and if the rotating speed is higher than 12,000 rpm, the dewatering rate will not significantly differ from that in the case in which the rotating speed is lower than 12,000 rpm, and thus the efficiency of dewatering will be reduced.
  • Step 8 is a drying step (S80).
  • Because the dewatered tryptophan sludge cake still has a high water content, the water content is lowered to 10% or less by hot-air drying to form powder. Before the sludge cake is dried in hot air, a process of washing the sludge cake and separating the washing water by centrifugation may further be performed. This powdering process provides high-purity tryptophan.
  • Experiment 1
  • Experiment on Change in Injection Rate of Sulfuric Acid
  • Experimental Conditions
  • Tryptophan concentration: 200 g/L;
  • NaOH concentration: 5 mol/L;
  • Initial pH: 14;
  • Sulfuric acid concentration: 30%;
  • Stirring speed: 300 rpm;
  • Reaction temperature: 25° C.; and
  • Injection rate of sulfuric acid: 0.5 mL/min, 2 mL/min, and injection at a time.
  • Experimental Results
  • As the injection rate of sulfuric acid decreased, the size of grains showed a tendency to become smaller. Also, as the reaction time increased, the particle size became smaller. For this reason, the reaction time should be short.
  • TABLE 1
    Particle size
    Microscope Cloud point
    PSA (μm) (μm) Time pH Final pH
    1 48.64 20-45 Immediately 7.6
    2 31 20-30  37 min 9.26 7.7
    3 12.49 10-20 110 min 10.3 7.6
  • For reference, FIGS. 6 to 8 are microscopic photographs of 1, 2 and 3 in Table 1 above.
  • Experiment 2
  • Experiment for Determination of Reaction Time
  • Experimental Conditions
  • Tryptophan concentration: 100 g/L;
  • NaOH concentration: 5 mol/L;
  • Initial pH: 14;
  • Sulfuric acid concentration: 30%;
  • Stirring speed: 300 rpm;
  • Reaction temperature: 25;
  • Amount and rate of injection of sulfuric acid: 100 mL & 16.7 mL/min; and
  • Other conditions: Neutralization to pH 7 followed by stirring for long time.
  • Experimental Results
  • The results of Experiment 1 indicated that tryptophan particles having a large particle size could be produced even when the reaction was performed for a short time. However, the results of Experiment 2 indicated that, when stirring was performed for a short time, small crystals were easily broken due to a weak bond therebetween. As shown in FIGS. 9 and 10 to 13, as the reaction time increased, the amount of crystals having an intermediate size decreased while the amount of large crystals showed a tendency to increase. However, a reaction time shorter than about 18 hours showed a uniform particle size distribution.
  • The recovery rate was about 95% or higher without significantly changing depending on the reaction time, suggesting that tryptophan precipitated within a short time.
  • Experiment 3
  • Experiment for Determination of Reaction Time
  • Experimental Conditions
  • NaOH concentration: 5 mol/L;
  • Tryptophan concentration: 10, 100 and 200 g/L;
  • Sulfuric acid concentration: 30%;
  • Stirring speed: 100 and 300 rpm;
  • Reaction temperature: 25° C.;
  • pH: 7; and
  • Reaction time: 6 hours.
  • Experimental Results
  • As shown in FIG. 14, as the concentration of tryptophan decreased, the particle size increased. As shown in FIG. 15, the purity was about 99% or higher in all the conditions, and as shown in FIG. 16, the recovery rate was about 75% in all the conditions. It can be seen that lowering the dissolution concentration of tryptophan is a method capable of inhibiting nucleation and that the method of the present invention is suitable for lowering nucleation. It is believed that as nucleation decreases, nuclei are attached to dissolved tryptophan to cause crystal growth.
  • Experiment 4
  • Experiment for Determination of Reaction Time
  • Experimental Conditions
  • NaOH concentration: 5 mol/L;
  • Tryptophan concentration: 10 g/L;
  • Sulfuric acid concentration: 30%;
  • Stirring speed: 100 and 300 rpm;
  • Reaction temperature: 25° C.;
  • pH: 7; and
  • Reaction time: 6 hours.
  • Experimental Results
  • As shown in FIGS. 17 to 19, as the stirring speed decreased, the particle size increased. The material of this Experiment is a sheet-like material comprising particles having a weak bonding strength therebetween. The results of the analysis indicated that the height of the sheet was 1 μm or less, and thus the crystal particles produced would be easily broken.

Claims (13)

1. A purification system comprising:
a solution storage tank configured to store a solution;
an ultrasonic disperser configured to ultrasonically disperse particles contained in the solution in the solution storage tank;
a stirrer configured to stir the solution stored in the solution storage tank;
a heating jacket provided outside the solution storage tank and configured to control the internal temperature of the storage tank;
an air compressor configured to suck the solution from the solution storage tank and send the sucked solution to a position next thereto; and
a continuous reactor configured to be supplied with the solution sent by the air compressor together with a solvent sent through a separate pathway and to stir the supplied solutions at high speed to continuously produce a reaction product having uniform particles.
2. A purification system comprising:
a solution storage tank configured to store a solution;
an ultrasonic disperser configured to ultrasonically disperse particles contained in the solution in the solution storage tank;
a stirrer configured to stir the solution stored in the solution storage tank;
a heating jacket provided outside the solution storage tank and configured to control the internal temperature of the storage tank;
an air compressor configured to suck the solution from the solution storage tank and send the sucked solution to a position next thereto; and
a filter cartridge configured to filter fine impurities contained in the solution sent by the air compressor;
a temperature controlling unit comprising a casing enclosing the filter cartridge, a heating medium filled in the casing, and a heater for heating the heating medium;
a continuous reactor configured to be supplied with the filtered solution that passed through the filter cartridge, together with a semi-solvent stored in a semi-solvent storage tank, and to stir the supplied solution and semi-solvent to produce a reaction product having uniform particles;
an organic material separator configured to be connected to a discharge port of the reactor and to separate a slurry-type reaction product, discharged from the continuous reactor, into an organic material and a liquid;
an organic material storage chamber configured to store the solid organic material separated by the organic material separator; and
an analysis and correction module configured to collect the liquid separated by the organic material separator, analyze whether or not the state of the collected liquid is normal, and correct process conditions into optimal conditions on the basis of the results of the analysis.
3. The purification system of claim 2, wherein the filter cartridge comprises a filter case and a material filled in the filter case, in which the filled material consists of one or a mixture of two or more selected from the group consisting of metal oxides, including activated alumina, silica, and titanium oxide, and natural stones, including activated carbon, bentonite, acid clay, and diatomaceous earth.
4. The purification system of claim 2, wherein the organic material separator is a centrifuge or a dewaterer.
5. The purification system of claim 1, wherein the continuous reactor comprises:
a cylinder that includes a reaction chamber configured to receive the filtered solution together with the semi-solvent, and has a semi-solvent injection port formed at the upper portion of the cylinder and configured to introduce the semi-solvent into the reaction chamber, and a solution injection port formed at the lower portion of the cylinder and configured to introduce the organic material solution into the reaction chamber;
a heating medium-filled chamber formed along the outer circumference of the reaction chamber and filled with a heating medium for controlling the temperature of the solution and semi-solvent received in the reaction chamber;
a plurality of partitioning plates configured to divide the space of the heating medium-filled chamber into a plurality of spaces and made of a thermal insulating material in order to block heat exchange between the heating media filled in the plurality of heating medium-filled chamber spaces;
a temperature controlling element configured to control the temperature of the heating medium filled in each of the heating medium-filled chamber spaces divided by the partitioning plates;
a stirring body rotatably provided in the cylinder and configured to stir the solution and semi-solvent in the cylinder;
a stirring motor disposed below the cylinder; and
a belt pulley and a belt, which connect the shaft of the stirring motor to one end of the stirring body so as to transfer power of the stirring motor to the stirring body.
6. The purification system of claim 5, further comprising a temperature sensor configured to sense the temperature of the heating medium in each of the heating medium-filled chamber spaces and transmit the sensed temperature to the analysis and correction module.
7. The purification system of claim 5, wherein the wall surface of the reaction chamber and the heating medium-filled chamber is coated with corrosion-resistant Teflon or made of hastelloy-C.
8. A purification system comprising:
a filter configured to filter out solids from a solution while allowing the solution to pass therethrough;
a solution storage tank configured to store the solution that passed through the filter;
an ultrasonic disperser configured to ultrasonically disperse particles contained in the solution in the solution storage tank;
a stirrer configured to stir the solution stored in the solution storage tank;
a heating jacket provided outside the storage tank and configured to control the internal temperature of the storage tank;
an air compressor configured to suck the solution from the solution storage tank and send the sucked solution to a position next thereto;
a continuous reactor configured to be supplied with the solution sent by the air compressor together with a solvent sent through a separate pathway and to stir the supplied solutions at high speed to continuously produce a reaction product;
a dewaterer configured to be connected to a discharge port of the continuous reactor and to separate a liquid from a slurry-type reaction product discharged from the continuous reactor; and
a dryer configured to dry a solid component separated by the dewaterer.
9. A method for purifying tryptophan using the purification system of claim 1, the method comprising:
allowing a tryptophan solution to pass through a filter before storage in a storage tank to remove solids having a size larger than a predetermined size;
introducing NaOH into the storage tank to adjust the pH of the tryptophan solution;
maintaining the temperature of the tryptophan solution in the storage tank at a predetermined temperature using a heating jacket provided outside the storage tank;
adding a polymer material to the tryptophan solution in the storage tank to increase the density of particles in the tryptophan solution;
supplying the tryptophan solution from the storage tank to a continuous reactor;
adding an acid solution to the tryptophan solution supplied to the continuous reactor to neutralize the pH of the tryptophan solution to thereby precipitate crystals;
dewatering the precipitated crystal particles by a dewaterer to separate the particles into a solid and a liquid; and
drying the solid of step (S70) in hot air.
10. The purification system of claim 2, wherein the continuous reactor comprises:
a cylinder that includes a reaction chamber configured to receive the filtered solution together with the semi-solvent, and has a semi-solvent injection port formed at the upper portion of the cylinder and configured to introduce the semi-solvent into the reaction chamber, and a solution injection port formed at the lower portion of the cylinder and configured to introduce the organic material solution into the reaction chamber;
a heating medium-filled chamber formed along the outer circumference of the reaction chamber and filled with a heating medium for controlling the temperature of the solution and semi-solvent received in the reaction chamber;
a plurality of partitioning plates configured to divide the space of the heating medium-filled chamber into a plurality of spaces and made of a thermal insulating material in order to block heat exchange between the heating media filled in the plurality of heating medium-filled chamber spaces;
a temperature controlling element configured to control the temperature of the heating medium filled in each of the heating medium-filled chamber spaces divided by the partitioning plates;
a stirring body rotatably provided in the cylinder and configured to stir the solution and semi-solvent in the cylinder;
a stirring motor disposed below the cylinder; and
a belt pulley and a belt, which connect the shaft of the stirring motor to one end of the stirring body so as to transfer power of the stirring motor to the stirring body.
11. The purification system of claim 10, further comprising a temperature sensor configured to sense the temperature of the heating medium in each of the heating medium-filled chamber spaces and transmit the sensed temperature to the analysis and correction module.
12. The purification system of claim 10, wherein the wall surface of the reaction chamber and the heating medium-filled chamber is coated with corrosion-resistant Teflon or made of hastelloy-C.
13. A method for purifying tryptophan using the purification system of claim 2, the method comprising:
allowing a tryptophan solution to pass through a filter before storage in a storage tank to remove solids having a size larger than a predetermined size;
introducing NaOH into the storage tank to adjust the pH of the tryptophan solution;
maintaining the temperature of the tryptophan solution in the storage tank at a predetermined temperature using a heating jacket provided outside the storage tank;
adding a polymer material to the tryptophan solution in the storage tank to increase the density of particles in the tryptophan solution;
supplying the tryptophan solution from the storage tank to a continuous reactor;
adding an acid solution to the tryptophan solution supplied to the continuous reactor to neutralize the pH of the tryptophan solution to thereby precipitate crystals;
dewatering the precipitated crystal particles by a dewaterer to separate the particles into a solid and a liquid; and
drying the solid in hot air.
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