CN100506852C - Polymer treatment - Google Patents

Polymer treatment Download PDF

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Publication number
CN100506852C
CN100506852C CNB2003801026649A CN200380102664A CN100506852C CN 100506852 C CN100506852 C CN 100506852C CN B2003801026649 A CNB2003801026649 A CN B2003801026649A CN 200380102664 A CN200380102664 A CN 200380102664A CN 100506852 C CN100506852 C CN 100506852C
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gas
container
purifying vessel
particulate polymers
vessel
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CN1711286A (en
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F·库赞
B·沃尔沃思
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Ineos Manufacturing Belgium NV
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Ineos Manufacturing Belgium NV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/168—Removing undesirable residual components, e.g. solvents, unreacted monomers; Degassing

Abstract

A process for the separation of volatile material from particulate polymer which has been substantially freed from unreacted monomer in an earlier separation step, comprising (a) feeding the particulate polymer to a purge vessel, optionally causing it to move through the vessel in substantially plug-flow mode, (b) heating the particulate polymer in the purge vessel to a temperature greater than 30 DEG C but insufficiently high to cause the particles to become agglomerated, and/or maintaining the polymer at a temperature in this range in the purge vessel, (c) feeding gas to the purge vessel counter-current to the movement of the particulate polymer to remove volatile material therefrom, (d) removing the particulate polymer from the purge vessel, wherein substantially all of the heating of the particles which occurs in the purge vessel is accomplished by preheating the gas fed into the purge vessel.

Description

The processing of polymkeric substance
The present invention relates to from particulate polymers to remove the method for volatile materials and relate more specifically to remove polymkeric substance, polymer powder or the particulate polymer material from granulation the volatile constituent of trace.
Though the present invention can be applied to any particulate polymers in principle, be used for from wherein removing volatile matter, following specification sheets main reference is removed the method for volatile matter from particulate polyolefin.
By alkene, for example ethene, propylene or higher alkene C for example 4To C 12The catalyzed polymerization of alpha-olefin or the polyolefine of copolymerization are before being processed into useful goods, usually through removing the technology of most of unreacted monomer.The technology that this class is used to remove unreacted monomer generally includes monomer separation and reclaimer, wherein when polyolefine at first when polymerization reactor is removed, the most of unreacted monomer relevant with polyolefin products separated.The method that is used for initial monomer separation and recovery depends on the particular technology that polyreaction is used.For example, in gas phase (being total to) polymerization of alkene, polyolefin products is fine powder normally, the atmosphere fluidization or the stirring of its involved gaseous monomer.For example by separation comprise unreacted monomer, with some gas at least and the Continuous Flow of the particulate polymer product of some liquid coexistence randomly; Reduce pressure and circulation volatile constituent to reactor; And, can from gas phase process, separate and reclaim monomer with rare gas element for example nitrogen or purifying carbon dioxide polymeric constituent.
Therefore, in this manual, volatile materials can be for example one or more monomers itself, oligopolymer, any solvent that is used for polymerization or thinner, catalystic material or by the additive in its deutero-product, the polymerization (for example molecular weight regulator), be present in any impurities in raw materials of using in the polymerization or be used for the material of the movable part of lubricated reactor.This class volatile matter also may produce the degraded or the interaction of auto-polymerization component itself and/or its product.In final polymer, exist this class volatile matter normally undesirable, and may cause for example in goods, producing noxious odor by its manufacturing, perhaps may in the food of using the container package of making by this polymkeric substance, produce and pollute, perhaps in from the water of drinking-water pipe wire system, produce and pollute.The existence of inflammableness volatile materials also may produce the danger of catching fire or exploding.Therefore equally, this class volatile materials may have toxicity, pungency or other undesirable pharmacological properties, removes that they are normally wished or or even necessary.
Volatile matter in the polymkeric substance also may produce between the polymkeric substance granulation stage, for example because the thermal destruction of polymkeric substance itself, perhaps owing to the degraded of the additive that uses in the prilling process.
GB-A-1272778 relates to the method for removing volatile constituent from particulate olefin polymers, this polymkeric substance is by for example vapour phase polymerization production of ethene or propylene of monomer, this method keeps this bed strenuous exercise to carry out by the bed with inert gas flow processing polymkeric substance in treatment zone simultaneously, described polymkeric substance has 10 to 5000 microns mean diameter, and the temperature of described rare gas element is at least+80 ℃ to the temperature that is lower than at least 5 ℃ of polymkeric substance crystallite fusing points.
EP-A-0047077 relates to the method for removing unpolymerized gaseous monomer from the solid olefin polymer, this method comprises polymkeric substance (for example granular form) is transported to purifying vessel, polymkeric substance is purged gas stream with the adverse current rare gas element to be contacted, so that the monomer gas stripping that volatilizes in the polymkeric substance is gone out, and rare gas element-monomer gas that a circulation part obtains flows to purifying vessel.
The present invention relates to from the polymkeric substance of particulate polymers material, the particularly preparation of the catalyzed polymerization by organic monomer, to remove the volatile materials of trace, unreacted monomer, oligopolymer or other volatile constituents improved method of solvent or degraded product for example for example.
Particularly, the present invention relates to the method for from particulate polymers material, preferred particulates polyolefine, removing volatile materials, described polymer materials has carried out at least a unreacted monomer methods that is used to separate, for example method of describing among GB-A-1272778 and the EP-A-047077 in advance.
The invention provides the method that is used for from particulate polymers separating volatile material, described particulate polymers has been removed unreacted monomer in large quantities in separating step early, and described method comprises:
(a) particulate polymers is fed to purifying vessel, and make its with plug flow pattern basically by described container,
(b) in described purifying vessel, particulate polymers is heated to above 30 ℃, but be not high enough to cause particle that agglomerant temperature takes place, and/or in described purifying vessel, polymkeric substance is remained under the temperature of this scope,
(c) gas feed is arrived purifying vessel,, from purifying vessel, removes particulate polymers with from wherein removing volatile materials,
Wherein, all basically particulate that carries out in purifying vessel heating are finished by the gas that preheating is fed in the purifying vessel.
In this manual, " plug flow pattern " refers to that particulate polymers is such mode by the mobile of relevant container, wherein exists seldom or not to have axial mixing when particulate polymers passes container, therefore guaranteed that the particulate residence time is uniform substantially." plug flow " is sometimes referred to as " mass flow " in the art, when particularly research mobile is the motion of solid particulate materials especially like this.Another kind of definition is, the flow characteristics that particulate polymers has in purifying vessel should make the standard deviation of the residence time preferably be not more than the mean residence time of particulate polymers in purifying vessel 20% and even more preferably no more than 10%.
The gas of preferred feedstock in the purifying vessel with the motion charging upstream of particulate polymers.
The particulate polymers that volatile materials is therefrom removed in hope can be the polymkeric substance or the granulated material of for example polymer powder, granulation, and it has carried out initial monomer separation step.When in the presence of particulate polymers is containing the catalyzer of transition metal, preparing, preferably before handling polymkeric substance according to the inventive method with any relict catalyst deactivation that is present in the polymkeric substance.The preferred particulates polymkeric substance is polyolefin powder, pellet or the granulated material by the polymerization of one or more monomers 1-alkene or (being total to) polymerization preparation, described polymerization can be carried out in mutually at gas phase, liquid phase (for example using so-called " particle form " polymerizing condition) or solution, perhaps from high temperature and high pressure method (being commonly referred to " high pressure method ").Selectively, particulate polyolefin can be the polyolefine that for example has been converted into another particle form by granulation or granulation.The preferred particulates polyolefine is a pelleted polymer, more preferably pelleted polyolefin.Therefore, equally preferably, before entering purifying vessel, particulate polyolefin is passed through forcing machine and granulation.
The amount that is present in the volatile materials (except the water) in the polymkeric substance that is fed in the purifying vessel, when passing through chromatogram (KWS method, when carbon-hydrogen chromatogram) measuring, preferably be not more than 500ppm (parts per million by weight), more preferably no more than 300ppm and even more preferably no more than 100ppm.After according to processing of the present invention, the amount that is present in the volatile materials (except the water) in the polymkeric substance that leaves purifying vessel, when passing through chromatogram (KWS method, when carbon-hydrogen chromatogram) measuring, preferably be not more than 300ppm (parts per million by weight), more preferably no more than 200ppm and even more preferably no more than 100ppm.After according to processing of the present invention, the amount that is present in the volatile materials (except the water) in the polymkeric substance that leaves purifying vessel, compare with the amount of volatile materials (except the water) in being present in the polymkeric substance that enters purifying vessel, the value of its reduction, when passing through chromatogram (KWS method, when carbon-hydrogen chromatogram) measuring, greater than 300ppm (parts per million by weight), more preferably greater than 500ppm.
This obvious reduction of volatile materials content has remarkable favorable influence to the organoleptics property of final polymkeric substance.The present invention can reduce the taste grade of high density polyethylene(HDPE), according to the KTW method, reduces to 1-1.5 from 2-3.
The particulate polymers that is fed to purifying vessel can be preheated before entering purifying vessel, perhaps can only be heated in purifying vessel itself.Particulate polymers can be fed to preheating container off and on, continuously, once or in batches.Preferred its charging continuously.Preferably, particulate polymers with plug flow pattern basically by described preheating container.Particulate polymers is heated the temperature that reaches and can be at least 30 ℃ in preheating container, and the highest 70 ℃ or higher, and condition is that temperature is not high enough to cause particle that agglomerant temperature takes place.As standard roughly, this temperature should not be higher than following about 5 ℃ of vicat softening temperature.Particulate polymers preferably uses the pneumatic transport technology to be fed to heating container.If the use preheating container, as required, can equip therein make Purge gas with the equipment of moving into upstream of particulate polymers by container.As required, High Temperature Gas, for example Re nitrogen can be used for heating the particulate polymers in preheating container.In addition, preheating container uses conventional industrial equipments, for example steam or hot water jacket to heat.
When particulate polymers was granulation, as required, this pellet can directly be fed to purifying vessel from tablets press, perhaps was fed to heating container (if use).Pellet directly is fed to purifying vessel or heating container can further be saved energy requirement from tablets press, if particularly still comprise waste heat from granulation process from the pellet of tablets press.Can optimize this energy-conservation process, for example, make pellet quenching after, keep hot state, still be unlikely to Tai Re and cause the pellet agglomeration by suitably regulating the temperature of quench water.
Particulate polymers is fed to purifying vessel in any mode easily, for example uses pneumatic transport, perhaps utilizes the gravity feeding device, wherein uses suitable charging valve between raw material source and purifying vessel.Preferably particulate polymers is fed to purifying vessel continuously.
The residence time of particle in container is identical for all particles basically.Can use conventional industrial equipments to obtain plug flow.Therefore, the preferred purifying vessel that has smooth internal walls and in the major portion of its length, have the homogeneous cross section that uses.For example, outlet at purifying vessel, can use the cross section of conical butt or other gradual change, condition is that the angle of discharge cone is calculated, so that guarantee the piston flow quality (this angle can be calculated by the shearing test result, and depends on the character of processed particulate polymers) of container.The principle of plug flow is well-known in the art, and can adopt these principles easily to design proper device.Purifying vessel is preferably tubular and have a cross section of homogeneous basically.Major portion can adopt the form of the pipe that for example has square or circular cross section.Purifying vessel most preferably is the cylindrical vessel of arranged perpendicular, has conical portion in its bottom, and it tapers to the outlet of the polymkeric substance that is positioned at the container bottom.Preferred purifying vessel vertically disposes.Most preferably, purifying vessel has uniform cylindric cross section on the major portion of its length, and has the length that doubles its diameter at least, in order to help to guarantee piston flow.
In one embodiment, by selecting special valve to control relief outlet and in cylindrical vessel, obtain piston flow.This valve is the form that is positioned at the resupinate circular cone on the conical butt pedestal, limits annular channels whereby when valve is opened.Such scheme can prevent the center quick drain of polymkeric substance via purifying vessel, otherwise may cause non-piston flow.When using such scheme operation, preferably valve is opened discontinuously, but opens off and on; Have been found that this is for guaranteeing that piston flow is best.Preferably, valve was opened in the time of half; The typical cycle is to open in 1-3 minute, closes in the time of same amount, though correct time will depend on the size of container certainly.
The size of flow velocity and purifying vessel suitably is provided with, make the residence time of particulate polymers in purifying vessel be in about 0.5 to 16 hour, preferably 2 to 16 hours, more preferably in 6 to 12 hours the scope.For some application, require at least 10 hours.
The heated temperature of particulate polymers is suitably at least 30 ℃, preferably at least 50 ℃, most preferably at least 70 ℃ or higher in purifying vessel, and condition is that this temperature is not enough to cause particle agglomeration.As mentioned above, as standard roughly, this temperature preferably is not higher than following about 5 ℃ of vicat softening temperature.For example, if vicat softening temperature is 80 ℃, then the heated top temperature of particulate polymers should preferably not be higher than 75 ℃.Being density at particulate polymers is 0.945kg/m at least 3The situation of high density polyethylene(HDPE) under, the Heating temperature in purifying vessel is preferably in 70 to 100 ℃ of scopes.On the other hand, be under the more low-density multipolymer situation at particulate polymers, for example the multipolymer of ethene and senior 1-alkene for example has 0.915 to 0.945kg/m 3Density in the scope, described temperature preferably are in 60 to 80 ℃ of scopes.Under any circumstance, this temperature must be not high to making particle agglomeration.Do not observe this principle, can cause polymkeric substance in preheating or purifying vessel, to stop up, or even in these containers, form unmanageable bulk.
This particulate polymers can use any suitable promotion means, for example use Archimedean screw device or only pass through purifying vessel under action of gravity.Yet preferably along with solid is discharged in the bottom from purifying vessel, particulate polymers moves under action of gravity.Preferably with the purifying vessel thermal insulation during purifying, to keep heat.
Preferably, gas is to pass through purifying vessel upstream with flowing of particulate polymers." adverse current " is meant that gas crosses particle or flow through facing to particulate.Gas is heated before in being expelled to purifying vessel.Usually gas is air.Yet, as required,, can in air, replenish other gas, for example nitrogen or carbonic acid gas if for example wish to reduce any potentially dangerous of catching fire or exploding.Yet the present invention is applied to reduce the volatile matter in the particulate polymers usually, and the volatile content in the wherein said particulate polymers has been lower level.Therefore, be present in from purifying vessel, come out purge gas stream in the level of volatile matter be no more than about 5 mg/litre gases usually, preferably be no more than about 1 mg/litre gas.Especially preferred content is less than 150g/m 3
Gas is maintained at such level by the flow velocity of particulate polymers, promptly is lower than to cause the level of the interruption of particulate polymers piston flow.This is significantly less than and causes the fluidised flow velocity of particulate polymers.
Under the pelleted polymer situation, do not cause that plug flow destroys the situation that the gas flow rate allowed is much higher than powdery polymer usually.For enough heating to polymkeric substance are provided, the flow velocity of gas is preferably at least 80 liters/hours/square centimeters of cross sections, and this numerical value measures radially by purifying vessel mobile direction that (unit is abbreviated as l.hr hereinafter crossing over particulate polymers - 1Cm -2).The Peak Flow Rate that can allow and not interrupt piston flow is about 150l.hr -1Cm -2
Though all gas can be introduced purifying vessel in the position of approaching the purifying vessel bottom and upwards blow by particulate polymers, this need use significant pressure.We have found that if most of high-temperature gas is introduced purifying vessel in the position of approaching top (particulate polymers is from entering) here, only introduce in the bottom than the gas of small proportion, removing of volatile matter can be effective just.Introducing gas in the position of approaching container top needs much lower pressure, and this is the same with the gas of introducing very little mass rate in the bottom.It is believed that this scheme is just effectively, in case because polymkeric substance is heated, only need be with less air flow quantity in order to remove volatile compound.Therefore, obtaining to have the most effective means of gas by the hot particulate polymers of its mobile, is to introduce in the position of approaching container top to keep the needed most of gas of described polymkeric substance.Therefore, at least a portion that preferably enters the gas of purifying vessel enters at one or more points that approach the top of purifying vessel; And each of preferably described one or more points is positioned at such level, makes that the particle that is less than 20% volume in container is in this more than level when container comprises the particulate polymers of maximum.Equally preferably, no more than 20%, more preferably no more than 10% point in the bottom of approaching container of total mass that enters the gas of container enters.In this case, be generally at least 0.5 liter/hour/square centimeter of cross section at the flow velocity that approaches the gas that container bottom enters, this value cross over the footpath of particulate polymers by the flow direction of purifying vessel upwards mensuration (this unit is abbreviated as l.hr hereinafter -1Cm - 2).Therefore, for example, what be particularly useful is that flow velocity is 2 to 10l.hr -1Cm -2Gas enter in purifying vessel bottom.Further preferably, near the part of the gas of introducing the top of purifying vessel directly is discharged to the central authorities of container, randomly by axially extended pipeline.This helps avoid container intermediary cold spots.Preferably, the mass rate that is introduced directly into container intermediary gas is about 20-40% of the mass rate of the gas of introducing container side in identical level.Usually, be to be understood that, the exact position of gas inlet point, in the gas flow and the purifying vessel size of each inlet point, under various individual cases, calculate, and depend on the processed particulate polymers and the flow of polymkeric substance, uniform gas distributes and effective heating/devolatilization so that obtain.
Though the heating of all basically particulate polymers is carried out by means of high-temperature gas, but the present invention does not get rid of the possibility that has some boosting equipment, near the localized heat exchanger placed in the middle purifying vessel top for example is to guarantee the suitable heating at the container center place.
Pressure in the purifying vessel can be the pressure of any hope, approach the barometric point (absolute pressure that for example is higher than 1 crust a little but in fact use, but be lower than 200mbarg) pressure normally satisfied because this has been avoided using the expensive pressurized vessel and the needs of gas blower.In fact, Purge gas is introduced the slight raising that purifying vessel causes pressure usually.
In purifying vessel, volatile materials diffuses out from particulate polymers and enters gas stream, and to be carried to the zone that particulate polymers is fed to container upstream with moving into of particulate polymers.The suitable pipeline equipment of preferred use is discharged gas from purifying vessel.The expellant gas that comprises volatile matter flare tower can be fed to,, suitable recovery unit can be fed to if perhaps for example wish to reclaim any volatile constituent.Often find that the concentration of volatile matter is (to be lower than 150mg/m so for a short time 3), to such an extent as to can directly be discharged in the atmosphere from the gas of purifying vessel.The preferred processing condition that keep, make the concentration of any inflammable volatile materials in the vent gas from purifying vessel be lower than the gas flammability limit 25%, preferably be lower than 5% of gas flammability limit.For example, by reducing the concentration that one or more following parameters can reduce this class volatile materials: the volume that particulate polymers occupied in (1) purifying vessel, (2) particulate polymers by purifying vessel flow velocity and (3) purifying vessel in the temperature of particulate polymers; Perhaps by improving gas can reduce this class volatile materials by the flow velocity of purifying vessel concentration.
Particulate polymers is suitably removed from purifying vessel by means of gravity simply.Yet this can promote by means of particulate matter industry handling equipment, for example motorized valve or the rotation gas lock of routine.The preferred mechanical device for transferring comprises the speed change device for transferring, for example variable speed motorised valves or power screw.This container preferably is equipped with the amount of detection particulate polymers wherein or the equipment of level, for example the equipment of settled particulate polymers level in the detection receptacle.Preferably, the equipment of the amount of particulate polymers or level and for example variable bit rate device for transferring associating in the detection receptacle are so that the volume of particulate polymers keeps constant in the container.This associating can for example obtain by electronic installation or mechanism.
By after the purifying vessel, it remains heat usually at particulate polymers, and transfer to storage facility or further handle or process before may need to cool off.For example, under the polyethylene situation, if wish to use the moving handling equipment of dilute phase or dense phase gas particulate polymers is transferred to storeroom, then preferably before shifting, it is cooled to be lower than about 65 ℃, common 40-60 ℃ temperature, to be reduced in the possibility that forms so-called " edge fluffing (angel hair) " in the pneumatic transport pipeline.If you are using, the equipment that is used for the cooling particulate polymkeric substance can comprise for example conventional industrial particle cooling apparatus.Can use air or water cooling.For example, hot particulate polymers can be intermittently or continuous regime be fed to the gas fluidized bed water cooler.Be used for the refrigerative air and can introduce the charging of the warm air that will be introduced into purifying vessel subsequently, so that reduce heating cost.
In one embodiment, refrigerating unit can join the bottom of purifying vessel, so that save facility investment; In this case, described design must guarantee at least to have piston flow everywhere at purifying vessel before entering cooling segment.Randomly, the gas that being used in the introducing purifying vessel removed volatile matter passes through container bottom at first when not heating, help the particulate polymers of cooling heat this its, is heated simultaneously.Then this gas further is heated to the temperature that needs, and then introduces purifying vessel, to contact with polymkeric substance in the predetermined position.
As mentioned above, preferably utilize equipment that particulate polymers is taken out from purifying vessel, to take out polymkeric substance continuously.Similarly, preheating container and/or cooling vessel preferably are equipped with the equipment of continuous taking-up polymkeric substance, for example utilize motorized valve or electric screw.Preferably, device for transferring is the speed change device for transferring, for example uses variable speed motorised valves and/or shaking table.Described container preferably is equipped with the wherein amount of particulate polymers or the equipment of level, for example equipment of the amount of settled particulate polymers or level in the detection receptacle of detecting.Preferably, the equipment of the amount of particulate polymers or level and for example variable bit rate device for transferring associating in the detection receptacle are so that the volume of particulate polymers keeps constant in the container.This associating can for example obtain by electronic installation or mechanism.
As required, particulate polymers can also be the plug flow pattern by flowing of cooling vessel.Particulate polymers can obtain by means of standard industry equipment by the plug flow of cooling vessel.
Suitably be used for particulate polymers of the present invention and can be for example polymer powder, it is the direct products of polymerization technique, condition is that this polymer powder has been removed unreacted monomer basically in separating step formerly, the powder of being produced by the gas fluidised bed polymerisation of alkene for example is perhaps from being used for producing granuloplastic powder in the technology of liquid diluent polymerization single polymerization monomer.Preferred polymer beads is a polymeric aggregate, and it is well known in the art as the standard prod that is used for the processable polymer goods.The size of polymer beads suitably is 0.1 to 10mm, preferred 2 to 7mm.For example, the polymeric aggregate that is used for the processing plastic goods is in 3 usually in the 6mm scope.
Preferred described polymer beads comprises one or more polyolefine.Preferred polyolefine is polyethylene, polypropylene and ethene and one or more C 3To C 12The multipolymer of alpha-olefin.The example of this base polymer is high density polyethylene(HDPE), medium-density polyethylene, linear low density polyethylene and very low density polyethylene (VLDPE).
In one embodiment of the invention, aforesaid method carries out after the treatment step that is used for reducing the gas dilution dosage that is included in raw polymer slurry, and this raw polymer slurry is discharged from polymerization reactor.When polymerization reactor is discharged, raw polymer slurry is to comprise Macrodilution agent, the form of the material of unreacted olefinic type monomers in a small amount, and it can comprise a spot of catalyzer, promotor, other hydro carbons and any other material, and this depends on the manufacturing process (below be generically and collectively referred to as " pollutent ") of use.After pressure release, the polymerizable raw material resin enters the above-mentioned decontamination chamber under about barometric point, and wherein nitrogen is used to these pollutents are purged away.Comprise nitrogen, thinner, olefinic type monomers and other is because of the different material of technology from the purge vent stream of this step.In order to minimize the amount of transferring to the thinner the hydro carbons decontamination chamber from olefin polymerization reactor, and randomly maximize the recovery to described thinner, carried out following steps from described decontamination chamber:
Discharge the slurries that comprise polyolefine and thinner from polymerization reactor continuously;
Pressure release with described slurries makes diluent evaporates, forms polyolefin/gas mixture;
Continuously described polyolefin/gas mixture is discharged in the collection container;
Open the inlet valve of the concentrator vessel that also comprises outlet valve with a kind of like this method, make the described polyolefin/gas mixture of pre-determined volume be transferred to described concentrator vessel;
Close the inlet valve of described concentrator vessel;
Open the outlet valve of described concentrator vessel with a kind of like this method, make described polyolefin/gas mixture be transferred in the hydro carbons decontamination chamber.
The advantage of above-mentioned steps sequence is, replace directly from polymerization reactor-correspondingly directly polyolefin/gas mixture is transferred to the decontamination chamber with a large amount of gas from polymerization reactor, in polymerization reactor and decontamination chamber, correspondingly between collection container and decontamination chamber, use concentrator vessel from collection container.Therefore the amount of transferring to the gas of decontamination chamber from polymerization reactor is minimized.Usually, polymerization reactor is under the high pressure (10-40 crust), and the decontamination chamber is under the pressure that approaches barometric point.The discharging gas of discharging from collection container is few more, and the gas that must be recycled and be pressurized to the elevated pressures that needs in polymerization reactor is few more.Use aforesaid concentrator vessel, can reduce the amount of the gas that is transferred to low-tension side (being the decontamination chamber).For example, when Trimethylmethane is used as the polymeric thinner, and be reduced to about 10 whens crust when the pressure in second step of the inventive method, the amount that is transferred to the gas of decontamination chamber is lowered to about 2.5 weight %.Therefore, compressor can have reduced size, thus they purchase with process cost lower.In addition, because the amount of unreacted monomer that must be recycled and solvent is less, the downstream recycle unit can be less and energy expenditure is lower.Preferably select to be, replace using a concentrator vessel, two concentrator vessel of use in parallel.
In round-robin first part, first concentrator vessel is full of with polyolefin/gas mixture, and the inlet valve of first concentrator vessel cuts out.Before first concentrator vessel is flushed into the decontamination chamber, the pressure compensation valve that connects two concentrator vessel is opened.The gas that is included in first concentrator vessel is transferred to second concentrator vessel, and the pressure in two concentrator vessel is for approximately identical.Then the pressure compensation valve between the concentrator vessel is closed, and first concentrator vessel is emptied the decontamination chamber.Pressure in first concentrator vessel is reduced to the pressure in the decontamination chamber, and the pressure in second concentrator vessel is higher than the pressure in the decontamination chamber, but is lower than the pressure in the collection container, promptly low about 30-50%.
In second part of round-robin, use polyolefin/gas mixture to be full of second concentrator vessel, and the pressure between two concentrator vessel obtain balance by opening the pressure compensation valve that connects two concentrator vessel from collection container.Second concentrator vessel will finally be flushed into the decontamination chamber.
Use the method for two concentrator vessel in parallel, further reduced from polymerization reactor-correspondingly transfer to low-tension side, be the amount of the gas of decontamination chamber from collection container.For example, when Trimethylmethane is used as the polymeric thinner, and be reduced to about 10 whens crust when the pressure in the step (b), the amount of transferring to the gas in the decontamination chamber is lowered to about 1 weight %.These numerals depend on the tap density of polymkeric substance and the density of gas.Further select to comprise the following step that is used to handle from the purge vent stream of decontamination chamber:
-purge vent stream the compression and the cooling of self-purification chamber in the future causes the partial condensation of logistics, whereby logistics has been divided into enrichment monomeric condensation portion and enrichment the uncooled part of Purge gas;
Uncooled part is divided into two parts,
The first part of uncooled part is recycled to the decontamination chamber;
In separating unit, handle second part of uncooled part, produce the purge gas stream and the mixture flow of enrichment more;
In the bottom of decontamination chamber or in by-level, the purge gas stream recirculation of the unitary enrichment of self-separation in the future and
The unitary mixture flow of self-separation in the future by they being turned back to the purge vent stream of the upstream of compression section, and is recycled to condensing steps.
The method of handling purge vent stream is very economical.Really because from the amount of the monomer of decontamination chamber and other recyclable product and concentration less than in the traditional method those, therefore do not need very large equipment, i.e. compression/cooling and separating unit.Their acquisition expenses and process cost are less.
In addition, the first part of uncooled part is recycled directly to the decontamination chamber, has further reduced size, cost and the energy expenditure of equipment.
Condensing steps preferably carries out under the pressure between about 8 to 20 crust; When Trimethylmethane is used as when being used for the polymeric thinner, described pressure is usually between 12 to 16 crust.Condensing steps preferably also carries out under the temperature between-30 to+50 ℃; When Trimethylmethane was used as the polymeric thinner, described temperature was usually between 5 and 15 ℃.
Separating unit can comprise film separation unit, low temperature separation process unit, absorptive unit or the like.Under the low temperature separation process situation, described unit comprises distillation tower, and it has the condenser of operation at low temperatures, for example-50 to-100 ℃.
The separation that utilizes film is preferred.The preferred film that uses carries out, the very fast infiltration component that this film has-be alkene-be about at least 5 with respect to the selectivity of other component-be Purge gas.
Should be noted in the discussion above that to be used for minimizing the aforesaid method of transferring to the gas volume of hydro carbons decontamination chamber from polymerization reactor, can be applied to any polymkeric substance manufacturing processed.
Illustrate the present invention referring now to accompanying drawing, wherein Fig. 1 diagramming is used to reduce first embodiment of equipment of the volatile content of linear high-density polyethylene (HDPE) pellet, the HDPE powdered preparation of this pellet from producing by the gas fluidised bed polymerisation of ethene.
Fig. 1 shows purifying vessel 1, from the forcing machine (not shown) via inlet pipe 3 to the Continuous Flow of feed pellets wherein, any excessive pellet is transferred to the buffering feed bin via pipeline 5.In this certain embodiments, introduce pellet with 6 tons/hour speed, and purifying vessel 1 have diameter and the 150m of 4.5m 3Internal volume.Warm air from pipeline 14 is introduced at point 12, is heated by means of the steam from pipeline 16.Air upwards blows by pellet, and makes purifying vessel remain on 90 ℃ temperature.Guarantee piston flow by outlet valve, it is the form of resupinate cone.In this specific embodiment, valve is not opened continuously, but once opens and closes 2 minutes.Find that in this scheme, such situation has guaranteed piston flow.The pellet of handling is discharged to hopper 18, enters cooling vessel 20 then, and it is cooled to 40-60 ℃ by means of the water from pipeline 22.At last, cooling pellets is discharged into air conveyor pipeline 24.
In Fig. 2, shown similar scheme, from forcing machine via inlet pipe 3 continuously to purifying vessel 1 charging.In this embodiment, the speed of pellet charging is 30 tons/hour, and purifying vessel 1 has 700m 3Than internal volume, and discharge and warm air are supplied with both different systems.From the warm air of pipeline 14,, introduce at the point 12 that separates and 13 by means of steam heating from pipeline 16.In this certain embodiments, the relative rate of supply be the point 12 places be 17kg/s and the point 13 places be 1kg/s.Should be noted in the discussion above that a little 12 and 13 is many inlets, the representative of 3-5 inlet usually, described inlet centers on the diameter of purifying vessel on identical horizontal plane spaced apart.The warm air of introducing larger proportion at point 12 has guaranteed that pellet is heated satisfactorily when entering purifying vessel; Can provide other inlets, warm air is incorporated into the center of container, so that guarantee uniform heating at identical horizontal plane.Have been found that introduce suitable airflow means in the bottom and only need little flow at point 13 places (at the relatively large pressure of these needs) at the top of container.As in the embodiment in figure 1, the temperature in the purifying vessel is maintained at 90 ℃.The residence time of HDPB pellet is generally 10-12 hour.Also be different from Fig. 1 from the mode of container 1 discharging.Replace the internal valve scheme, continue discharging, guarantee to have piston flow by the size of calculating purifying vessel and the cone angle of part 15 by opening 17.As previously mentioned, the pellet of processing enters cooling vessel 20, and it arrives 40-60 ℃ by means of the water cooling from pipeline 22.The refrigerative pellet is discharged to air conveyor pipeline 24 then.
Embodiment 1
In the logistics of pellets of high density polyethylene, carried out the method for as above describing in conjunction with Fig. 1.Following table 1 has shown the content of the volatile materials (except the water) that exists in the polymkeric substance that enters purifying vessel and has handled the residual content in back according to the present invention, it is by chromatographic determination (the KWS method that pellet is measured, carbon-hydrogen chromatogram is measured the highest C16 down at 200 ℃).As seen, can obviously reduce volatile materials content by method of the present invention: can obtain to surpass the reduction of 500ppm.
Table 1-volatile materials content
Before the processing (ppm) After the processing (ppm) Reduce (ppm)
546 195 351
496 89 407
550 94 456
646 98 548
732 143 589
601 122 479
456 83 373
532 90 442
543 172 371
621 114 507
649 143 506
564 121 443
552 116 436
474 142 332

Claims (12)

1. be used for from the method for particulate polymers separating volatile material, described particulate polymers has been removed unreacted monomer basically in separating step early, and described method comprises:
(a) particulate polymers is fed to purifying vessel, and make its with plug flow pattern basically by described container,
(b) in described purifying vessel, particulate polymers is heated to above 30 ℃, but be not high enough to cause particle that agglomerant temperature takes place, and/or in described purifying vessel, polymkeric substance is remained under the temperature of this scope,
(c) gas feed is arrived purifying vessel,, from purifying vessel, removes particulate polymers with from wherein removing volatile materials,
Wherein, basically all particulate that carries out in purifying vessel heating are finished by the gas that preheating is fed in the purifying vessel, and at least a portion gas that is fed in the purifying vessel enters container at the one or more points that more approach container top for the distance bottom.
2. the process of claim 1 wherein that described gas is fed to purifying vessel upstream with the motion with particulate polymers.
3. the method for claim 1, wherein enter at least 80% the entering approaching described one or more points that container top is on the horizontal plane of total gas couette of described container, make that when container comprises the particulate polymers of maximum the particle volume less than 20% in the container is positioned at this above water.
4. the process of claim 1 wherein that being not more than of the gas total mass that enters container 20% enters container in the position of approaching container bottom.
5. the process of claim 1 wherein that being not more than of the gas total mass that enters container 10% enters container in the position of approaching container bottom.
6. the process of claim 1 wherein and the part of the gas that enters purifying vessel on the horizontal plane identical, directly be discharged into the centre of container with the inlet point of gas when one or more points near container top enter.
7. the method for claim 1, wherein enter the part of the gas of purifying vessel, on the horizontal plane identical with the inlet point of gas when one or more points near container top enter, directly be discharged into the centre of container, directly enter the mass rate of the intermediary gas of container, be the 20-40% of the mass rate of the gas that on identical horizontal plane, enters container side.
8. the process of claim 1 wherein that particulate polymers is the form of pellet.
9. the process of claim 1 wherein that from purifying vessel discharging is included in its bottom and has the Frusto-conical part of opening, the valve of resupinate cone form is installed thereon, when described valve is opened, limit annular channels whereby.
10. the method for claim 1, wherein discharging is included in its bottom and has the Frusto-conical part of opening from purifying vessel, the valve of resupinate cone form is installed thereon, when being opened, described valve limits annular channels whereby, and because the opening and closing of valve, the discharging of being undertaken by described valve is intermittently.
11. the process of claim 1 wherein at least a portion that is fed to the gas in the purifying vessel to be used to heat, by preheating at least in part from particulate polymers.
12. the process of claim 1 wherein described at least a portion that is fed to the gas in the purifying vessel, by its with make it pass through purifying vessel before particulate polymers contacts, be used to from the heat of particulate polymers and by preheating at least in part.
CNB2003801026649A 2002-10-30 2003-10-27 Polymer treatment Expired - Lifetime CN100506852C (en)

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