CN1497011A - Method of deaggre gating solution and removing micro particle from polyethylene glycol terephthalate and regeneration method of wed filtering material - Google Patents
Method of deaggre gating solution and removing micro particle from polyethylene glycol terephthalate and regeneration method of wed filtering material Download PDFInfo
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- CN1497011A CN1497011A CNA03164953XA CN03164953A CN1497011A CN 1497011 A CN1497011 A CN 1497011A CN A03164953X A CNA03164953X A CN A03164953XA CN 03164953 A CN03164953 A CN 03164953A CN 1497011 A CN1497011 A CN 1497011A
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Abstract
Provided is a method for inexpensively and simply removing finely divided particles having an average particle diameter of 1-500 [mu]m from a polyethylene terephthalate solution suppressing a loss of the solution to a minimum without generating a bulk waste material. The method for removing the finely divided particles comprises depolymerizing the polyethylene terephthalate with ethylene glycol to obtain an ethylene glycol solution of bis(2-hydroxyethyl)terephthalate containing the finely divided particles having the average particle diameter of 1-500 [mu]m and passing the solution through a filter filled with a filter medium comprising a fiber of 3-20 dtex in a void rate of 70-98% to remove the finely divided particles. The used filter medium is back washed with the ethylene glycol which is the solvent in the depolymerization process and reused.
Description
Technical field
The present invention relates to from the method for polyethylene terephthalate depolymerization solution and removing micro particle and the renovation process that is used for the filter material of this method.In more detail, relate to and remove method particles contained in the ethylene glycol solution of two (2-hydroxyethyl) terephthalate that spent glycol obtains the polyethylene terephthalate depolymerization and the renovation process that is used for the filter material of this method.
Background technology
Polyethylene terephthalate extensively is used in fiber, film, resin formed article because good at aspects such as thermal property, physical property, chemical propertys, as in the bottle etc.And the polyethylene terephthalate that is used for these purposes is usually by making dimethyl terephthalate (DMT) or terephthalic acid and glycol reaction.At this moment, in order to satisfy the characteristic that requires of catalysts and purposes, use various additives, for example tinting material, matting agent, thermo-stabilizer, photostabilizer etc.
In recent years, the polyethylene terephthalate moulded product after the use, particularly the disposable use of pet bottle causes natural environment deterioration, becomes social concern, is therefore studying the method that it utilizes again always.And, as the material egr mode of one of this method, that is, the moulded product that reclaims is pulverized, laminate or fragment, with its washing, refining, be used further to the mode of shaping raw material, begun practical application.
In addition, as aforementioned one of the method for utilizing again, the chemical re-circulation mode is arranged, for example open put down in writing in the 2000-169623 communique such the spy, handle has been proposed by polyethylene terephthalate moulded product to using up, particularly pet bottle etc. recycles, obtain the fragment or the thin slice of thick polyethylene terephthalate, with it as raw material, it is refining that spent glycol is separated coalescence with it, obtains highly purified two (2-hydroxyethyl) terephthalate, then in the presence of catalyzer, make this two (2-hydroxyl ethyl ester) terephthalate polycondensation, make the method for polyethylene terephthalate.
But, in above-mentioned depolymerization solution, contain for example tinting material (as copper phthalocyanine class pigment etc.), matting agent (as titanium oxide etc.), other additive particulates such as (as silicon-dioxide, carbon blacks etc.) that in the polyethylene terephthalate moulded product, use.In addition, grade, generally use gac in order to remove to be coloured to, but its part often remaining, be mingled in the solution after the processing.In addition, if these particulates are mingled in the above-mentioned depolymerization solution, in operation after this, can produce a series of problem: cause and in pipeline etc., pile up and stop up, cause attached to the device internal surface to cause its efficient reduction, cause device wearing and tearing, and then separate out at thermal conductive surface and to cause that heat conduction is bad etc.In addition, if remaining, be mingled in goods two (2-hydroxyethyl) terephthalate, can produce the problem that quality product reduces.
According to the inventor's result of study, the particulate of pigment or gac is that the filter cartridge, porcelain filter, bag filter etc. of number μ m are difficult to remove fully these particulates with aperture for example from depolymerization solution in the wide particle diameter distribution range of about 1～500 μ m.On the other hand, using the membrane filter of the about 1 μ m in aperture or diatomaceous precoat filter is effectively to removing these particulates, but membrane filter costs an arm and a leg, and needs the occasion of exchange regenerating stopping up because of filter screen.In addition, use the precoat filter following problems: it is bigger that depolymerization solution is absorbed the loss that causes by precoated material, and owing to need the discharge of conversion, the precoating filter material layer of precoat filter to remove, wash and the operations of logical liquid, operability is poor, and discharges waste in a large number.
Summary of the invention
The object of the present invention is to provide a kind of loss of the depolymerization solution with polyethylene terephthalate to be suppressed to inferior limit, do not produce a large amount of wastes, cheaply and easily remove the method for the particulate of median size 1～500 μ m contained in this depolymerization solution.
Another object of the present invention is to provide a kind of in by the depolymerization solution that removes by filter polyethylene terephthalate during contained aforementioned particulate, the filter method that filtration velocity is bigger, the washing of filtering material is easy and filter life is long.
The filtering material that another object of the present invention is to provide a kind of washing to be used for removing at the contained aforementioned particulate of depolymerization solution of polyethylene terephthalate enables to reuse, thereby prolongs the filtering material method of life.
Other purposes of the present invention and advantage can be learnt from following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by the method from polyethylene terephthalate depolymerization solution and removing micro particle aspect the 1st, it is characterized in that, make the ethylene glycol solution of two (2-hydroxyethyl) terephthalate of the particulate that the depolymerization of polyethylene terephthalate spent glycol is obtained and contain median size 1～500 μ m, by filled the filtration unit of the filter material that constitutes by 3～20dtex fiber with 70～98% voidage, remove particulate.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by the renovation process of filter material aspect second, it is characterized in that, from logical liquid side when filtering ethylene glycol solution in the opposite direction, make ethylene glycol by the above-mentioned filter material that uses in the method for removing, this filter material is washed to the state that can reuse.
Description of drawings
Fig. 1 is the relation between the voidage of filter material and the superficial velocity that can remove the particulate in the solution.
Embodiment
The method according to this invention can be removed particulate with the speed that can fully adopt on the operation of chemical re-circulation from the depolymerization solution of polyethylene terephthalate.In addition, by the primary solvent with depolymerization solution is that ethylene glycol carries out backwash to the filter material that uses, washing ethylene glycol is recycled in the depolymerization operation, can be suppressed to inferior limit to the loss of process fluid, do not produce a large amount of wastes, cheaply and easily remove contained particulate in the depolymerization solution of polyethylene terephthalate.
The ethylene glycol solution of two among the present invention (2-hydroxyethyl) terephthalate is to be the ethylene glycol solution (the depolymerization solution of polyethylene terephthalate) of main solute with two (2-hydroxyethyl) terephthalate that spent glycol obtains the polyethylene terephthalate depolymerization.And this solution contains the particulate of median size in 1～500 mu m range.
Aforementioned polyethylene terephthalate for example is that the polyethylene terephthalate bits that produce in the manufacturing process of the polyethylene terephthalate moulded product (for example pet bottle, film, trevira etc.) that will reclaim or these moulded products or the forming process are pulverized the material (for example thin slice, particle etc.) that obtains.And this polyethylene terephthalate both can be homopolymer on chemical constitution; Also can be to make the third composition, for example m-phthalic acid, hexanodioic acid, cyclohexanedimethanol, 1, ammediol, 1,4-butyleneglycol etc., with small proportion, for example with respect to the total acid composition at 15 moles below the %, further 10 moles of multipolymers that the following copolymerization of % obtains.
Above-mentioned polyethylene terephthalate in the presence of the depolymerization catalyzer with excessive glycol reaction (depolymerization), forming with two (2-hydroxyethyl) terephthalate is the ethylene glycol solution of main solute.This depolymerization can be according to itself known method, for example specially opens the method for putting down in writing in the 2000-169623 communique and carries out.In this ethylene glycol solution two (2-hydroxyethyl) terephthalate was to the weight ratio of ethylene glycol preferably 1: 2～1: 10, more preferably 1: 3～1: 7, preferred especially 1: 3.5～1: 5.0.The ethylene glycol solution that is obtained by this depolymerization contains the particulate of following when the particulate that adds in the polyethylene terephthalate or moulded product are handled usually.
The composition of solute preferably contains more than the 75 weight % in the aforementioned ethylene glycol solution, even above two (2-hydroxyethyl) terephthalate of 85 weight %.
Aforementioned ethylene glycol solution among the present invention contains coloring components mostly, preferably implements decolouring with gac usually for this reason and handles.In addition, at this moment in order to improve the efficient of decolouring and handling with gac, be preferably in this decolouring processing before, carry out following filtration treatment.And, after this decolouring is handled,,, preferably carry out following filtration treatment in order to improve the efficient of back operation owing in filtrate, sneak into small amount of activated.As described below carrying out handled in this decolouring,, ethylene glycol solution is heated to two (2-hydroxyethyl) terephthalate of solute or the temperature that its oligopolymer is not separated out that is, and preferred 50～100 ℃, more preferably 65～90 ℃ and maintain under this temperature and carry out.And, as above-mentioned gac, can exemplify " ダ ィ ャ ホ-プ 008 " that Mitsubishi chemical Co., Ltd produces etc.With respect to the consumption of gac, the logical liquid measure of ethylene glycol solution is 50～200 times of weight preferably, more preferably 70～140 times of weight.By carrying out this activated carbon treatment, can remove coloring components, but then, also be difficult to avoid remaining a spot of microgranular gac in ethylene glycol solution.
In the present invention, aforementioned ethylene glycol solution is maintained two (2-hydroxyethyl) terephthalate and oligopolymer is not separated out, and the temperature of particulate such as the pigment (for example copper phthalocyanine class pigment, titanium oxide, silica gel etc.) of contained median size 1～500 μ m or gac in can filtering solution, and under the said temperature condition, carry out filter operation.Specifically, depend on the kind and the occupied state of filter material, preferably, more preferably carry out under 65～90 ℃ the temperature 50～100 ℃ temperature.If this temperature is lower than 50 ℃, then two (2-hydroxyethyl) terephthalate and oligopolymer thereof are easy to separate out, and meeting of I'm afraid of these materials and particulate are removed from solution by filtering together, and in addition, because the viscosity of ethylene glycol increases, filtering operability is easy to reduction.On the other hand, if temperature is higher than 100 ℃, then the velocity of evaporation of ethylene glycol increases, and operability also can reduce, thereby not preferred.
The depolymerization solution of the polyethylene terephthalate among the present invention, promptly be the removing of particulate of median size 1～500 μ m contained in the ethylene glycol solution of main solute with two (2-hydroxyethyl) terephthalate, can adopt in natural filtration and the forced filtration (reduce pressure or add the filtration of depressing) any one mode to carry out, preferably adopt the forced filtration mode to carry out.The amount of the particulate matter that exists in the solution after aforementioned depolymerization reaction finishes is different because of the form (for example bottle, film, sheet material or fiber) as the polyethylene terephthalate of raw material, generally about 1～2000ppm.By improving ratio, the concentration of this particulate matter can be controlled at lower concentration as pet bottle that does not contain inert particle in the waste of raw material or film etc.On the other hand, decolour handle in order to make regeneration of activated carbon when the decolouring device is extracted a part out, perhaps when replenishing gac again, be mingled in the disposable concentration that reaches about 50ppm of concentration in the depolymerization solution for removing gac (particulate) that being coloured to grades uses, but reduce along with after the moving of depolymerization solution, be issued to stable in the concentration of about 5～10ppm.
Thereby, if the concentration of particulate matters such as aforementioned tinting material is controlled at lower value, even consistent with the concentration of micro activated carbon particle, also only be approximate number 10ppm, in addition owing to can be suppressed to this level, industrially can be suitable for the clarification filtration mode, thereby preferred.
Ethylene glycol solution of the present invention since with the higher ethylene glycol of viscosity ratio as solvent, and contain particulate as the particle that should remove with about 1 μ m particle diameter, therefore when it is filtered, little as the normally used hard coal of filtering material, sand, granulated glass sphere or garnet etc. owing to voidage, filtration velocity reduces, and filter life is also short, thereby be not suitable for.
The fiber that constitutes filter material of the present invention is 3～20dtex, the fiber of preferred 4～10dtex.The mean length of this fiber can change with filling mode, preferred 10～1000mm, more preferably 10～500mm, preferred especially 30～100mm.And the tensile strength of fiber is preferably more than the 3cN/dtex, further preferred 4～50cN/dtex.In addition, as long as can reach required voidage, this fiber both can curl, and also can not curl.Usually, the fiber (for example filler cotton) that is made of staple fibre curls, and the fiber that is made of long filament does not curl.Preferred 0.3～1.0 time/mm of number of crimp.The section form of these fibers is arbitrarily, can exemplify circle, trilateral, square, rhombus etc.In addition, fiber also can be middle real fiber, tubular fibre etc.More specifically can enumerate section form is the middle real fiber of justifying shape, hollow circle shape, middle real triangular shape, hollow triangular shape, hollow diamond shaped etc.Fiber is that synthon, natural fiber all can.
Fiber is the occasion of synthon, as the raw material that constitutes it, can enumerate for example polyester, polypropylene, polymeric amide, polyacrylic acid, ァ ラ ミ De, polyacrylic ester (Port リ ァ リ レ one ト), polyphenylene oxide, polyimide etc.Wherein, has the fiber of form retentivity when preferably not having reactivity or lacking reactivity and filtration treatment, for example polypropylene fibre, polyacrylic fibre etc. with solvent ethylene glycol; Superfluorescent fiber, for example ァ ラ ミ De fiber, polyacrylic fiber, polyphenylether fibre, polyimide fiber etc., more preferably polypropylene fibre etc.In addition, by the polymkeric substance that has with the characteristic of glycol reaction, polyester for example, the fiber of formation causes fiber to attenuate because of filtration treatment for a long time, can not keep the characteristic as filter material, will note when therefore using.But, the occasion that the filler cotton of trevira is used as filter material, the raw material that out of use filter material can be used as depolymerization supplies in chemical re-circulation.In this, trevira also is preferred filter material in the present invention.
Aforementioned filter material is with voidage 70～98%, and preferred 80～96% fill.In addition, this voidage voidage that is aforementioned ethylene glycol solution by the time to the filter material applying load.And, voidage when making this applying load reaches required value, can be by using the voidage adjustable plate of the wire netting that for example is provided with number (for example 4 orders), the consumption of adjusting filter material and this voidage adjustable plate position in filtration unit are (for example, the position height of adjustable plate then voidage increases, and low then voidage reduces) carry out.In addition, also preferably fill with following method.Fill aforementioned filter material in the filtration unit and should satisfy following relation, promptly when filtering, the diameter (D) of height of fiberfill fibers (L) and filtration unit concern L/D preferably 0.5～5, be more preferably 1～4, especially preferably 1.5～3.
In addition, more than the preferred particularly 20mm of L, more preferably more than the 50mm.
Fill method is so long as the not bias current on filtering layer of assurance filtrate gets final product, and method is any.For example, in the occasion of using the filler cotton, the logical fluidity back up pad (for example porous plate, wire netting, grid etc.) that supports the filter material fiber can be set at the liquid downstream side of filtration unit, with thereon suitably the filler cotton of mixed assemblage put into the belt of setting height and make in the net bag of suspention form, the top of the filter material layer of further packing in the net bag is provided with fiber stopper, treatment solution dispersion porous plate.In addition, according to the viscosity of the diameter and the solution of filtration unit, filler that also can thickness is different is cotton and fill as the big fiber combinations of the Young's modulus rate of material with superfluorescent fiber.
In addition, in the occasion of using long filament or yarn, preference is as yarn (straight yarn), the cloth gripper yarn of irregular implantation 10cm～1m length on metal net shaped porous plate, and the length of flocking is short in the bottom of porous plate, last minister, and in filtration unit, take in the flocking rod of mop shape.
For the filtration unit that uses in the methods of the invention, the filter material layer of filling both can be that individual layer also can be a multilayer.In addition, the filter material layer can be the mixture of the different fiber of length, dtex or raw material, also can be and the fibre blend that does not have to curl.In addition, length, dtex or the raw material of each filter material layer fiber of a plurality of filter material layers can be different, and each filter material layer also can comprise layer that curling fiber constitutes and the layer that does not have curling fiber to constitute.
In the present invention, as previously mentioned, make in the filtration unit of ethylene glycol solution by the filter material that constitutes by the synthon of having filled 3～20dtex with 70～98% voidage, remove the particulate of median size contained in this solution 1～500 μ m.The superficial velocity of ethylene glycol solution this moment in filtration unit can be got maximum.Below the preferred 60m/h of this superficial velocity, more preferably 13～56m/h.Ethylene glycol solution the method in the filtration unit of supplying to can be the method that descends of the top from filtering material, flow to the method on top from the bottom or supply with and from the whole bag of tricks such as method of central part extraction from two sides up and down.
According to the present invention, in order further to remove remaining slightly particulate, for example particle diameter for example can further filter filtering the filtrate that obtains by fibrous filter with sand-bed filter, membrane filter etc. less than the particulate of 1 μ m etc.Sand filter or membrane filter are compared with fibrous filter and are easy to stop up, but only have very small amount of particulate owing in the filtrate filtered in the present invention, so do not need frequently to change sand-bed filter or membrane filter etc. because of obstruction.
Fig. 1 represents the voidage of filter material and can remove relation between the superficial velocity of the particulate in the solution.In the chemical re-circulation process, preferably below the 60m/h, more preferably be 13～56m/h from the adoptable superficial velocity of relation of whole operating times, manipulation amount etc.As can be seen from Figure 1, adopt filter material of the present invention, when voidage 85%, superficial velocity reaches 32m/h, can remove particulate from depolymerization solution with the speed that can fully adopt in aforementioned operation.
The filter material that is made of fiber has the feature that can carry out regenerated from washing repeatedly in the present invention.The renovation process of preferred filter material be from the filtration of ethylene glycol solution the time logical liquid side in the opposite direction, make ethylene glycol by being used to remove the filter material of aforementioned particulate, and wash until the method that can reuse this filter material.At this moment, in the cotton mode of filler, use by filter material is put in the net bag as previously mentioned, be easy to wash mode washing and filtering material, or further from filtration unit, take out and wash, thereby the discarded of filter material reduced significantly with backwash.In addition, in the occasion of using long filament or yarn, behind the ethylene glycol solution and filtration of feeding specified amount,, can easily wash by from making the washings glycol flow to the filter material layer in the other direction.Thus, have the efficient that can improve filtration unit and the advantage of prolongs life.
In the washing of aforementioned filtering material, when washing from the other direction ethylene glycol being flow through, the voidage that preferably makes filtering material is more than 95%, further is more than 97%, makes interval between the fiber increase to when filtering 3～20 times.In addition, the occasion that the effect of backwash reduces after for example taking out filter material from washing device, is pushed, and extrudes ethylene glycol solution, washes with water in washing machine and removes dirt settling, and centrifugation is dewatered, and carries out drying under warm braw, can reuse.And, because of causing the compression of fiber, use recovers the occasion that weakens, by carrying out combing, also can recover.The washings of filtering material can directly supply in the depolymerization operation, preferably makes with extra care, and supplies to then in the depolymerization operation.
The present invention has following advantage.
(1) if filtering material by synthon, particularly polypropylene fibre, superfluorescent fiber constitute, even with respect to the ethylene glycol of 50～100 ℃ of temperature, also have sufficient erosion resistance.In addition, the filter material that is caused by wearing and tearing reduces reduction, so magnitude of recruitment is also few.
(2) because the voidage height of filter material under low filtration pressure, can carry out big flow and handle, filter life is long simultaneously.
(3) filter material can backwash (washing that washings is flow through from direction opposite when filtering), can utilize cheaply again.In addition, the occasion that reduces in the effect of backwash, take out filter material from washing device after, compress, extrude ethylene glycol solution, in washing machine, wash with water and remove dirt settling, dewater by centrifugation, under warm braw, carry out drying, can re-use.And, in the occasion that the compression recovery that causes fiber because of use weakens,, also can recover by carrying out combing.
Embodiment
For mode more specifically of the present invention is described, enumerate embodiment below.The present invention is not subjected to the qualification of these embodiment certainly.In addition, the characteristic in the example is measured with following method.
(1) superficial velocity
Logical liquid speed is used the m/hr representation unit divided by the filtration unit basal area of packed tower for example.
(2) voidage
The weight of the filter material that uses is obtained the volume V of filter material itself divided by the proportion of this filter material
0, obtain packing volume V from the internal diameter of filling jar and the packing height of filter material thereof on the other hand
tVoidage ε (%) obtains with following formula
ε(％)＝100×(V
t-V
0)/V
t
Embodiment 1
To put in the autoclave by thin slice 75kg, the ethylene glycol 420kg of the polyethylene terephthalate of about 8mm * 8mm of the mixture preparation of the non-staining pet bottle of the painted pet bottle of the 10 weight % that contain blue phthalocyanine pigment and 90 weight % and the crystallization 280g of sodium hydroxide, under agitation, under 218 ℃ of pressure 0.15Mpa, temperature, reacted 2 hours, with the polyethylene terephthalate depolymerization, be cooled to 85 ℃, obtain yellowish green depolymerization solution.
85 ℃ warm water chucks are installed on the SUS304 post of internal diameter 102.3mm, height 1000mm, the filler cotton that will be made of the polypropylene fibre of 6dtex is put into mesh bag, by regulating the filling amount and being provided with the height of voidage adjustable plate of 4 purpose wire cloths of SUS system, fill with voidage 85%, make L/D=2.Keep the liquid layer of 150mm height on filter material top, supply with aforementioned depolymerization solution simultaneously continuously, extract filtrate out from the extraction mouth of the 150 purpose wire cloths that have the cotton fluid stopping mouth of filler at front end.The superficial velocity of this moment is 32m/h.Filter yellowish green depolymerization solution 495kg (463 liters) through 1.8 hours, obtain xanchromatic filtrate.In Fig. 1, the relation of superficial velocity and voidage marks as a point.
In addition, in order to estimate aforementioned filtering effect, use the membrane filter of aperture 1 μ m that depolymerization solution 100ml is filtered, washing gained solid substance is also dry, measure the quality of solid substance, thereby obtain, be 63ppm by the pigment particle that removes by filter and the concentration of other insoluble particle.On the other hand, measure the concentration of obtaining pigment particle and other insoluble particle contained in the filtrate of depolymerization solution too, be 1.3ppm.
Then, prepare to have filled the post of gac in the post of internal diameter 500mm, height 1500mm, attemperation is so that the temperature of gac reaches 85 ℃, and the yellow filtrate that will use the filtration of aforementioned fibers filter material to obtain simultaneously supplies in the post, to the filtrate processing of decolouring.With with above-mentioned same method, this filtrate is passed in the post of the filler cotton that has refilled pet fiber with superficial velocity 32m/h, remove micro activated carbon particle contained in the filtrate.The concentration of contained micro activated carbon particle reduces to 0.6ppm with respect to the 47ppm before filtering in the filtrate after the filtration.
Embodiment 2
After using in embodiment 1 fibrous filter that uses 7 times repeatedly, the filter pressure that is in 1～6kPa level has before this surpassed 10kPa, therefore stops to filter.Improve the height of voidage adjustable plate, make voidage bring up to 95% or more after, fibrous filter sent into from top pushes air (5kg/cm
2G), discharge contained depolymerization solution in the filtering material.Afterwards, send into 80 ℃ 10 liters of warm ethylene glycol simultaneously and, extract out from the depolymerization solution input port on top roughly with the extruding air of amount from the filtrate outlet of bottom, carry out backwash after, voidage reaches 97%.Afterwards, send into the extruding air from top, discharge ethylene glycol residual in filter material.After this backwash operation carried out 3 times, flow into 8 liters ethylene glycol from top, discharge the residue that remains in the system.Further by sending into the extruding air, discharge the ethylene glycol that remains in the filtering material after, reduce the height of space adjustable plate, turn back to 85%.Use such regenerated fibrous filter, 1 the same enforcement is filtered with embodiment.Measure the concentration of removing pigment particle and other insoluble particle contained in the filtrate of gained depolymerization solution, be 1.5ppm, equal quality when confirmation can obtain and use new fibrous filter.
In addition, confirm that the washing ethylene glycol that produces can supply in the depolymerization operation once again in this operation after removing foreign matter.
Embodiment 3
According to the order identical with embodiment 1, to put in the autoclave by thin slice 75kg, the ethylene glycol 420kg of the polyethylene terephthalate of about 8mm * 8mm of the mixture preparation of the non-staining pet bottle of the painted pet bottle of the 5 weight % that contain blue phthalocyanine pigment and 95 weight % and the crystallization 280g of sodium hydroxide, under agitation, under 218 ℃ of pressure 0.15Mpa, temperature, reacted 2 hours, after the polyethylene terephthalate depolymerization, be cooled to 85 ℃, obtain yellowish green depolymerization solution.
85 ℃ warm water chucks are installed on the SUS304 post of internal diameter 102.3mm, height 1000mm, by regulating the filling amount and being provided with the height of the voidage adjustable plate of SUS system 4 order wire nettings, fill the filler cotton that the polyethylene terephthalate by 6dtex constitutes with voidage 88%, make L/D=2.Keep the liquid layer of 150mm height on the top of filtering material, supply with aforementioned depolymerization solution simultaneously continuously, extract filtrate out from the extraction mouth of the 150 purpose wire cloths that have the cotton fluid stopping mouth of filler at front end.The superficial velocity of this moment is 35m/h.Filter yellowish green depolymerization solution 495kg (463 liters) through 1.6 hours, obtain xanchromatic filtrate.In Fig. 1, the relation of superficial velocity and voidage marks as the b point.
In order to estimate aforementioned filtering effect, film filter with aperture 1 μ m filters depolymerization solution 100ml, and washing gained solid substance is also dry, measures the quality of solid substance, thereby obtain by the pigment particle that removes by filter and the concentration of other insoluble particle, be 42ppm.On the other hand, measure the concentration of obtaining pigment particle and other insoluble particle contained in the filtrate of depolymerization solution too, be 1.0ppm.
Then, prepare to have filled the post of gac in the post of internal diameter 500mm, height 1500mm, attemperation is so that the temperature of gac reaches 85 ℃, and the yellow filtrate that will use the filtration of aforementioned fibers filter material to obtain simultaneously supplies in the post, to the filtrate processing of decolouring.With with above-mentioned same method, this filtrate is passed in the post of the filler cotton that has refilled pet fiber with superficial velocity 35m/h, remove micro activated carbon particle contained in the filtrate.The concentration of contained micro activated carbon particle reduces to 0.8ppm with respect to the 45ppm before filtering in the filtrate after the filtration.
Embodiment 4
Order according to identical with embodiment 1 obtains depolymerization solution.
85 ℃ warm water chucks are installed on the SUS304 post of internal diameter 102.3mm, height 1000mm, by regulating the filling amount and being provided with the height of the voidage adjustable plate of SUS system 4 order wire nettings, fill the filler cotton that the polypropylene fibre by 4dtex constitutes with voidage 93%, make L/D=2.Keep the liquid layer of 150mm height on the top of filtering material, supply with aforementioned depolymerization solution simultaneously continuously, extract filtrate out from the extraction mouth of the 150 purpose wire cloths that have the cotton fluid stopping mouth of filler at front end.The superficial velocity of this moment is 49m/h.Filter yellowish green depolymerization solution 495kg (463 liters) through 1.2 hours, obtain xanchromatic filtrate.In Fig. 1, the relation of superficial velocity and voidage marks as the e point.
In addition, in order to estimate aforementioned filtering effect, use the membrane filter of aperture 1 μ m that depolymerization solution 100ml is filtered, washing gained solid substance is also dry, measure the quality of solid substance, thereby obtain, be 63ppm by the pigment particle that removes by filter and the concentration of other insoluble particle.On the other hand, measure the concentration of obtaining pigment particle and other insoluble particle contained in the filtrate of depolymerization solution too, be 1.8ppm.
Then, the post of gac has been filled in preparation in the post of internal diameter 500mm, height 1500mm, attemperation is so that the temperature of gac reaches 85 ℃, will use the aforementioned fibers filtering material to filter the yellow filtrate that obtains simultaneously and supply in the post, to the filtrate processing of decolouring.With with above-mentioned same method, this filtrate is passed in the post of the filler cotton of having filled polypropylene fibre with superficial velocity 49m/h, remove micro activated carbon particle contained in the filtrate.The concentration of contained micro activated carbon particle reduces to 0.9ppm with respect to the 47ppm before filtering in the filtrate after the filtration.
Comparative example 1
The same with embodiment 1; the preparation spent glycol is with the solution of polyethylene terephthalate depolymerization; with aforementioned depolymerization solution with 120 liters/h of flow velocity (superficial velocity 14.59m/h) be passed into filled median size 40～60 orders, voidage 47% silica sand so that in the post of L/D=2; particulate is blended in the filtrate, almost can not remove particulate from the depolymerization solution as stoste.Obtain clarifying filtrate in order to remove particulate, need make flow velocity is below the 35 liters/h (superficial velocity 4.26m/h).In Fig. 1, the relation of superficial velocity and voidage marks as a c.
Comparative example 2
The same with embodiment 1; the preparation spent glycol is with the solution of polyethylene terephthalate depolymerization; with aforementioned depolymerization solution with 120 liters/h of flow velocity (superficial velocity 14.59m/h) be passed into filled median size 0.2～0.3mm, voidage 39% granulated glass sphere so that in the post of L/D=2; particulate is blended in the filtrate, almost can not remove particulate from the depolymerization solution as stoste.Obtain clarifying filtrate in order to remove particulate, need make flow velocity is below the 17 liters/h (superficial velocity 2.07m/h).In Fig. 1, the relation of superficial velocity and voidage marks as a d.
Claims (12)
1. method from polyethylene terephthalate depolymerization solution and removing micro particle, it is characterized in that, in the filtration unit of the filter material that the ethylene glycol solution that makes two (2-hydroxyethyl) terephthalate that the depolymerization of polyethylene terephthalate spent glycol is obtained and contain median size 1～500 μ m particulate constitutes by the fiber of having filled with 70～98% voidage by 3～20dtex, remove above-mentioned particulate.
2. the method for claim 1 contains the above-mentioned particulate of 1～2000ppm concentration in above-mentioned ethylene glycol solution.
3. method as claimed in claim 1 or 2, the fiber of filter material is 4～10dtex.
4. as each described method in the claim 1～3, fiber is that fiber more than the 3.0cN/dtex constitutes by tensile strength.
5. as each described method in the claim 1～4, fiber is to be selected from least a in trevira and the polypropylene fibre.
6. as each described method in the claim 1～5, filter material is filled with voidage 80～96%.
7. as each described method in the claim 1～6, in filtration unit, packing height reaches 0.5～5 to the ratio of filtration unit internal diameter when making filtration with fiber filled.
8. as each described method in the claim 1～7, under 50～100 ℃ temperature, filter ethylene glycol solution.
9. as each described method in the claim 1～8, the superficial velocity of the solution that passes through is 13～60m/h.
10. the renovation process of a filtering material is characterized in that, logical liquor side makes ethylene glycol pass through the filter material that uses in the method for claim 1 in the opposite direction when filtering with ethylene glycol solution, with this filter material washing to reusable state.
11. method as claimed in claim 10, spent glycol when washing, be adjusted to the voidage of filter material 95% or more after, filtration ethylene glycol.
12. as claim 10 or 11 described methods, the fiber of filter material is to be selected from least a in trevira and the polypropylene fibre.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002229154 | 2002-08-06 | ||
| JP229154/2002 | 2002-08-06 | ||
| JP2003277334A JP2004083899A (en) | 2002-08-06 | 2003-07-22 | Removing method of finely divided particle from polyethylene terephthalate depolymerization solution and method for regenerating filter medium used for removing method |
| JP277334/2003 | 2003-07-22 |
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|---|---|
| CN1497011A true CN1497011A (en) | 2004-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA03164953XA Pending CN1497011A (en) | 2002-08-06 | 2003-08-06 | Method of deaggre gating solution and removing micro particle from polyethylene glycol terephthalate and regeneration method of wed filtering material |
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| JP (1) | JP2004083899A (en) |
| CN (1) | CN1497011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902677A (en) * | 2019-11-29 | 2020-03-24 | 金永哲 | Preparation method of activated carbon for decoloring adipic acid |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4595770B2 (en) * | 2005-09-28 | 2010-12-08 | 東レ株式会社 | Method for producing polyester-based thermobonding composite fiber |
| JP5186479B2 (en) * | 2007-02-23 | 2013-04-17 | 帝人株式会社 | Method for separating and removing dissimilar materials from polyester fiber waste |
| WO2010053051A1 (en) * | 2008-11-04 | 2010-05-14 | 栗田工業株式会社 | Filtration apparatus and water treatment equipment |
| EP4342941A1 (en) * | 2022-09-20 | 2024-03-27 | revalyu Resources GmbH | Process for recycling polyethylene terephthalate using a gradient in impurity concentration |
-
2003
- 2003-07-22 JP JP2003277334A patent/JP2004083899A/en active Pending
- 2003-08-06 CN CNA03164953XA patent/CN1497011A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902677A (en) * | 2019-11-29 | 2020-03-24 | 金永哲 | Preparation method of activated carbon for decoloring adipic acid |
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| JP2004083899A (en) | 2004-03-18 |
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