CN100513429C - Method for controlling sheeting in gas phase reactors - Google Patents

Abstract

Embodiments of the present invention relate to measuring and controlling static in a gas phase reactor polymerization. In particular, embodiments relate to monitoring carryover static in an entrainment zone during gas phase polymerization to determine the onset of reactor discontinuity events such as chunking and sheeting. Embodiments also relate to monitoring carryover static to determine the need for effective additions of continuity additives that minimize reactor static activity and thereby preventing discontinuity events.

Description

The method of the skinning in the control Gas-phase reactor

Technical field

Embodiment of the present invention relate to the electrostatic method of measuring and controlling in the gas-phase polymerization reactor.Especially, embodiment of the present invention relate to usually in the polymerization of adopting metalloscene catalyst, the new position of monitoring in whole gas-phase polymerization reactor carry static (carryoverstatic), to determine that the reactor interrupt event for example lumps and the method for the beginning of skinning.Embodiment of the present invention also relate to the static that carries at these new positions of monitoring, with determine whether need to add significant quantity at utmost to reduce reactor static active and especially carry electrostatic continuity additives (continuity additive), thereby prevent or at utmost reduce the method for this interrupt event.

Background

Skinning and caking are to have perplexed industrial gas-phase polyolefin to produce the problem in many years of reactor.This problem is characterised in that and forms the solid mass polymkeric substance on reactor wall.These solid mass or polymkeric substance (skinning) finally fall down and drop into the conversion zone from wall, they disturb fluidisation there, stop up product offtake, and force reactor down-time usually so that clean, in these incidents any one can be called as " interrupt event ", and it interrupts the operate continuously of polymerization reactor usually.Term " skinning, caking and/or fouling " though in this article synonym use, the differing appearance of similar problem can be described, under each situation, they can cause the reactor interrupt event.

At least two kinds of multi-form skinning take place in Gas-phase reactor.The skinning of these two kinds of forms (or type) is described to wall skinning or vault skinning (dome sheets), depends on the position that they form in reactor.The wall skinning is gone up at the wall (general vertical component) of conversion zone and is formed.The more higher position of vault skinning in reactor, on the conical part of vault, or formation (Fig. 1) on the snaphead of reactor head.

When with Ziegler-Natta catalyst generation skinning the time, it forms in the bottom of reactor usually, is called as the wall skinning.Ziegler-Natta catalyst can form the vault skinning, but rare.But under the situation of metalloscene catalyst, skinning can be in any position or these two kinds of positions take place; That is to say, wall skinning and vault skinning can take place.

Under the situation of metallocene catalyst system, the vault skinning especially bothers.Typical Metallocenic compound generally is described to contain one or more parts (normally cyclopentadienyl deutero-part or structure division) of transition metal atoms that can be bonded in and combines with transition metal in 4,5 or 6 families that are selected from the periodic table of elements or group of the lanthanides and the actinide elements.

A feature that is difficult to control skinning under the situation of metalloscene catalyst is their uncertain static proneness.For example, EP 0 811 638A2 have described the metalloscene catalyst that can occur unexpected unsettled static charge characteristic after secular stable behavior.

At with use the relevant reactor disruption of metalloscene catalyst, developed the multiple technology that allegedly can obtain improved operability.For example, US patent No.5,283,218 have discussed and have been used to prepare the fouling tendency with attenuating and the better various operation or the methods of supporting of the metallocene catalyst system of operability, this patent disclosure the prepolymerization of metalloscene catalyst.US patent Nos.5,332,706 and 5,473,028 discloses the particular technology that is used for forming by " initial stage dipping " catalyzer.US patent Nos.5,427,991 and 5,643,847 disclose the Chemical bond of non-coordination anion activator and carrier.US patent No.5,492,975 disclose the metallocene catalyst system of polymkeric substance combination.US patent No.5,661,095 disclose metalloscene catalyst have been supported method on the multipolymer of alkene and unsaturated silane.The open WO 97/06186 of PCT discloses after forming metalloscene catalyst and has removed inorganic and method organic impurity.WO 97/15602 discloses the metal complexes that supports easily.WO 97/27224 discloses and formed the method that supports transistion metal compound in the presence of the unsaturated organic compound with at least one terminal double link.

Other people have discussed to be used to improve with the successional different process of the reactor of metalloscene catalyst and conventional Ziegler-Natta catalyst and have changed.For example, WO 97/14721 discloses by unreactive hydrocarbons being joined the method for the particulate that suppresses to cause skinning in the reactor.US patent No.5,627,243 disclose the distribution plate that is used for gas fluidized bed reactor.WO96/08520 discloses and has avoided scavenging agent is incorporated into method in the reactor.US patent No.5,461,123 disclose the method for using sound wave to reduce skinning.US patent No.5,066,736 and EP-A1 0 549 252 disclose active retarding agent (activityretarder) be incorporated in the reactor to reduce the method for agglomerate.US patent No.5,610,244 disclose make-up monomers have been fed directly into more than bed in the reactor to avoid fouling and to improve the method for polymer quality.US patent No.5,126,414 disclose the method that adopts oligopolymer removal system to be used to reduce the distribution plate fouling and the polymkeric substance that does not contain gel is provided.Multiple other known method that is used to improve operability is arranged, comprise coating polymerization unit, controlled polymerization speed (especially when starting) and repacking reactor design and all ingredients is injected in the reactor.

As for all ingredients is injected in the reactor, use static inhibitor as if to have very much prospect also to become the theme of many publications as technology " continuity additives ".For example, EP0453116A1 discloses static inhibitor has been incorporated in the reactor method with the amount that reduces skinning and agglomerate.US patent No.4,012,574 discloses the surface active cpd that will have perfluoroalkyl joins in the reactor to reduce the method for fouling.WO 96/11961 disclose as the component of catalyst-loaded system be used for reduce gas phase, slurry mutually or the fouling of liquid polymerization method and the static inhibitor of skinning.US patent Nos.5,034,480 and 5,034,481 disclose the reaction product of conventional Z-N titanium catalyst and static inhibitor, are used to produce ultrahigh-molecular ethylene polymer.For example, WO 97/46599 discloses the application of soluble metal cyclopentadienyl catalyst in the gas phase process that adopts the soluble metal cyclopentadienyl catalyst, and wherein said soluble metal cyclopentadienyl catalyst is fed to the poor district of polymerization reactor, is used to produce tactic polymer.WO97/46599 is also open, and the catalysagen materials flow for example can contain anti-scaling or static inhibitor

163 (from ICI Specialty Chemicals, Baltimore, Md. is purchased).

US patent No.5,410,002 disclose the catalyst system that uses conventional Z-N titanium/magnesium to support, and wherein the static inhibitor of selecting are directly joined in the reactor to reduce fouling.The amount of static inhibitor is described to depend on the size distribution of polymkeric substance or formed polymkeric substance, and an example of static inhibitor is ATMER163, but discloses the method for the amount of dynamic adjustments or optimization static inhibitor.

US patent No.4,978,722 disclose the method that is used to prepare the propylene-alpha-olefin segmented copolymer, a kind of compound that wherein will be selected from aromatic carboxylic acid ester, phosphorous acid ester (phosphorous ester), unsaturated dicarboxylic acid diester, tertiary amine and the acid amides joins in the gas phase of polymerization reactor, thereby suppresses the formation of low-molecular weight polymer and prevent that polymkeric substance is attached on the reactor wall.But at US patent No.4, not mention the measurement of electrostatic activity in 978,722, not mention the method for the amount of the compound that optimization is added in order preventing to adhere to yet.

US patent No.5,026,795 discloses static inhibitor and liquid vehicle has been joined in the polymeric area of gas-phase polymerization reactor.Preferably, with static inhibitor and mixing diluents, and be incorporated in the reactor by the carrier that comprises comonomer.Disclosed preferred static inhibitor be with

The mixture of polysulfones, polymerized polyamines, sulfonic acid and toluene sold and contained by 450 trade mark by Octel Starreon.According to the amount that discloses static inhibitor is very important.Specifically, must there be competent static inhibitor to avoid polymkeric substance to be attached on the reactor wall, must makes poisoning of catalyst but be unlikely to many.US patent No.5,026,795 is also open, 1,000,000 of the polymkeric substance of being produced that the amount of preferred static inhibitor is by weight/about 0.2-5 (ppmw); Yet, the not open method of optimizing the level of static inhibitor according to the reactor condition that can measure.

More than EP 0 811 638 A2 of Lun Shuing disclose and used metalloscene catalyst and active cocatalyst in polymerization process in the presence of static inhibitor, also disclose the use of ATMER 163.EP 0 811 638 A2 also disclose the whole bag of tricks that is used to introduce static inhibitor, most preferably static inhibitor are sprayed in the fluidized-bed of reactor.Summarizing disclosed another kind of method is to add static inhibitor and support or the liquid catalyst materials flow, as long as catalyzer is not subjected to having a strong impact on or not poisoned by static inhibitor of static inhibitor.EP 0 811 638 A2 provided the catalyzer that wherein supports in being incorporated into reactor before slurrying and when using the non-catalyzer that supports, static inhibitor is introduced directly into example in the reactor in mineral oil.Several feet position measurement static more than the distribution plate of fluidized-bed itself.Preferably, in response to for example variation of electrostatic elevated levels, add static inhibitor off and on.

Though developed the use that many methods are controlled the skinning problem of metalloscene catalyst and investigated continuity additives, this problem still continues to exist.The use meeting that the reason that this problem continues to exist is a continuity additives is with the reduction of catalyst efficiency and productivity.The injection of additive did not have accurately coupling with the transient state (this can indicate undesirable " reactor interrupt event ") that stops reactor static with regard to frequency and/or amount when, the catalyst efficiency and the catalyst productivity that reduce had taken place.

The Another reason (with the root that perhaps is this problem) that the skinning problem of metalloscene catalyst continues to exist is that the warning in advance that lacks this incident (is annotated: EP0 811 638 A2 in above the 6th section).With the technology instrument of any previously known and/or use, comprise the conventional electrostatic probe that uses up to now, most of skinning incidents of metalloscene catalyst seldom or under the situation of nothing indication are in advance taking place.(conventional electrostatic probe is as this paper and US 4,855, described in 370, is positioned at those probes of 1/4 to 3/4 of the above reactor diameter in distribution plate top.) this conventional instrument lacks the indication that obtains the index that can measure in advance, it has proposed significant challenge to the effort of the skinning problem (interrupting with the reactor that is caused) of searching and correcting the reaction of using metallocene catalyst.

US 4,532,311st, and one of document that the reactor skinning is described is provided at first.This patent has at first been described and used the skinning of Ziegler-Natta catalyst is the result's of fluidized-bed static electrification important discovery.(uncertain it whether be the good idea of describing these instruction characteristics, unless it is clear and definite).Patent US 4,855,370 afterwards combines the device of the electrostatic level in the electrostatic probe of ' 311 files and the controlling reactor.At US 4,855, under 370 the situation, control electrostatic device is water to be joined in the reactor (with the amount of the 1-10ppm of ethylene feed).Proved that this method is effective for Ziegler-Natta catalyst, but invalid for metalloscene catalyst reaction or reactor.

For many years, the understanding to the reason of metalloscene catalyst skinning is hindered owing to lacking the detecting instrument that is fit to.Especially, be used for the electrostatic probe (so-called conventional electrostatic probe is arranged on the reactor wall as mentioned above) of Ziegler-Natta catalyst can not be effectively in the reaction of metallocene catalyst with adopt the reactor of this reaction that the warning or the notice of skinning or caking are provided.With popular response device electrostatic probe, the wall skinning of metalloscene catalyst and vault skinning take place under the situation that does not have in advance (or simultaneously) indication usually.This can find out in Fig. 7, Fig. 7 shows in pilot plant, compares with other electrostatic probe position that has shown response (that is the static more than zero), before the wall skinning incident of using metalloscene catalyst, (routine) reactor static probe is not response basically.

Therefore, advantageously, a kind of like this polymerization process that adopts metalloscene catalyst is arranged, this method can operate continuously, has the reactor operability (be defined as and generally do not have the skinning or the caking that may cause the reactor interrupt event to take place) of raising.Also very advantageously be, a kind of like this reactor condition based on easy mensuration arranged for example the static of each position of reactor assembly is active to have a more polymerization process of the tendentious operate continuously of fouling/skinning of stable catalyst productivity and attenuating, it need be solved by embodiment of the present invention.

General introduction

Belong to imagination we the working of an invention scheme row be between polymerization period the monitoring generation of static electricity to avoid or at utmost to reduce the method for reactor interrupt event, described method comprises: adopt the one or more mensuration at least one recirculation conduit electrostatic probe or at least one the annular disc probe to carry static.

Another embodiment comprises to prevent or to reverse by the amount of the skinning of the polymkeric substance that polyreaction was produced of at least a alkene that at least a continuity additives is incorporated into method in the reactor assembly, wherein this polyreaction is carried out in reactor assembly, this reactor assembly comprises fluidized-bed reactor, entrainment zone, be used to introduce the catalyzer feeding device of the catalyst system that can produce polymkeric substance, be used for introducing independently the continuity additives feeding device of at least a continuity additives with catalyst mixture, be used for monitoring the device of the static activity level of entrainment zone, this method comprises: allow at least a alkene and catalyst body tie up in the fluidized-bed reactor and contact under polymerizing condition; Before polyreaction begins, during or any time afterwards continuity additives is incorporated in the reactor assembly; Static activity level in the monitoring entrainment zone; And regulate the amount be incorporated into the continuity additives in the reactor assembly, so that the static activity level in the entrainment zone is remained on 0 or near 0.In this method, catalyst system comprises metallocenes or conventional transition-metal catalyst, and this method can be a gas phase process, and the continuous production polymkeric substance, and monomer comprises ethene or ethene and one or more alpha-olefins.In the method, catalyst system comprises metallocene catalyst system, and the device that wherein is used for measuring the static activity level of entrainment zone comprises one or more at least one recirculation conduit electrostatic probe, at least one annular disc probe, at least one distribution plate electrostatic probe or at least one the reactor top electrostatic probe.At least a continuity additives comprises that one or more are selected from the compound in alkoxylated amines, carboxylate salt, polysulfones, polymerized polyamines, sulfonic acid class or their combination.Perhaps at least a continuity additives comprises the ethoxylation stearic amine, and perhaps at least a continuity additives comprises aluminum stearate, and perhaps at least a continuity additives comprises aluminium oleate.Perhaps at least a continuity additives comprises the mixture of following component: the 1-decene-polysulfones that exists with the concentration of the 5-15wt% of mixture, the N-butter-1 that exist with the concentration of the 5-15wt% of mixture, the reaction product of 3-diaminopropanes and Epicholorohydrin, the Witco 1298 Soft Acid that exists with the concentration of the 5-15wt% of mixture, and the hydrocarbon solvent that exists with the concentration of the 60-88wt% of mixture.At least a continuity additives is introduced off and on, and/or at least a continuity additives is introduced as the slurry in hydrocarbon liquid or as the solution in hydrocarbon liquid.At least a continuity additives can also be present in via catalyst charge and is incorporated in the catalyst mixture in the reactor assembly, and the amount of this at least a continuity additives in fluidized-bed reactor remain on the concentration of 1-50ppm, is benchmark in the weight of the polymkeric substance produced in fluidized-bed reactor.

Another embodiment comprises a kind of polymerization process, and described method comprises: allow ethene and the polymerization in Gas-phase reactor in the presence of one or more metalloscene catalysts of one or more alpha-olefins; By the static activity in the monitoring device monitoring Gas-phase reactor; In response to offset from zero or about zero the active monitoring device of the described static of measurement, one or more continuity additives of significant quantity are applied in the polymerization process, so that this static activity turns back to zero or approximately zero.

Another contemplated embodiment is a gas phase polymerization process, wherein lowers or eliminate the static activity that produces in the entrainment zone of Gas-phase reactor, and described method comprises: allow ethene and the polymerization in the presence of metallocene catalyst system of one or more alpha-olefins; Adopt the one or more mensuration entrainment zone static activity at least one recirculation conduit electrostatic probe, at least one top electrostatic probe, at least one annular disc electrostatic probe or at least one the distribution plate electrostatic probe, prerequisite is if by by the active offset from zero of the static of one or more probe assays, with the significant quantity that effectively reduces or eliminate offset from zero one or more continuity additives are joined in the Gas-phase reactor so.

Another contemplated embodiment is a gas phase polymerization process, and described method comprises: in the presence of metallocene catalyst system with ethene and the polymerization in Gas-phase reactor of one or more alpha-olefins; Static activity in the monitoring reaction device, this monitoring comprise one or more at least one conventional electrostatic probe, at least one recirculation conduit electrostatic probe, at least one top electrostatic probe, at least one annular disc electrostatic probe, at least one distribution plate electrostatic probe or their combination; Wherein receive ampere/cm by active the differing ± 0.5 of the static of at least one mensuration at least one recirculation conduit electrostatic probe, at least one top electrostatic probe, at least one annular disc electrostatic probe or at least one the distribution plate electrostatic probe with the static activity of measuring by conventional electrostatic probe ²More than.

Another contemplated embodiment be in adopting the Gas-phase reactor of metalloscene catalyst, activator and carrier with the method for ethene and one or more alpha-olefin copolymers, described method comprises: in the presence of metalloscene catalyst, activator and carrier with one or more mixing in ethene and 1-butylene, 1-hexene or the 1-octene; By the static that carries in the one or more monitoring reaction devices at least one recirculation conduit electrostatic probe, at least one top electrostatic probe, at least one annular disc electrostatic probe or at least one the distribution plate electrostatic probe; Being selected from least a continuity additives in one or more of alkoxylated amines, carboxylate salt, polysulfones, polymerized polyamines, sulfonic acid class or their combination by use will carry static and remain on zero or approximately zero, this at least a continuity additives is present in the reactor with the amount of 10-40ppm, is benchmark in the weight of the polymkeric substance produced by polymerization.

Description of drawings

Fig. 1 shows the synoptic diagram of typical Gas-phase reactor.

Fig. 2 shows an example of popular response device electrostatic probe.

Fig. 3 shows the example of at least one recirculation conduit electrostatic probe.

Fig. 4 shows XCAT ^TMEZ100 vault skinning incident.

Fig. 5 shows four vault skinning incidents of XCAT EZ 100.

Fig. 6 shows the distribution plate static of XCAT EZ 100.

Fig. 7 shows XCAT ^TMThe wall skinning incident of HP 100.

Fig. 8 show XCAT HP 100 wall skinning incident carry static secretly.

Fig. 9 shows skin temperature and the additive flow of XCAT HP100.

The static that Figure 10 shows XCAT HP 100 distributes and additive flow.

Figure 11 shows the Octastat 3000 with XCAT HP 100

Skin temperature distribute.

Figure 12 shows and uses the Octastat 3000 with XCAT HP 100

Static distribute.

Describe

We are surprisingly found out that, by changing the active position of static (electric current of practical measurement unit surface) of practical measurement in the polymerization reactor, we can detect and the therefore for example beginning of skinning or caking of prophylactic response device interrupt event, especially for for the polymerization of metalloscene catalyst.In addition, we can stablize or eliminate the reactor interrupt event, are defined as skinning, caking or fouling here.Especially, we have found that for vapour phase polymerization, a large amount of static is by (understanding as common at granules of catalyst of carrying secretly and/or the resin particle carried secretly, the particle that what is called is carried secretly, we are meant in the emulsion zone that is not included in reactor and therefore are those particles in the outside of fluidized-bed) cause with the friction contact of other metal component in wall and the reactor recirculation system.We are called " carrying static " with this static.Now, carry static by discovery and mensuration in embodiments of the invention, solved known persistent problem (wherein known skinning and caking can not be predicted by popular response device electrostatic probe) metalloscene catalyst.Can carry static to this in position as herein described and monitor, and use conventional means or technology to be controlled, this so that reduce, prevent or eliminated skinning, caking or fouling.

The frictional electrification of solid particulate (or frictional electricity) is known in the literature.Generally, when two kinds of differing materials contact closely, can produce static.Differing materials can be two kinds of different metals (conductor), two kinds of different insulative bodies (exemplary is wool and amber rod), perhaps conductor and isolator.Under the situation of gas-phase polymerization reactor, static is obtained by the friction contact of the carbon steel (conductor) of polyvinyl resin and granules of catalyst (two kinds of isolators) and reactor wall.

The basic driver power of frictional electrification is the differences of two kinds of materials to the avidity of electronics.Material electron gain with higher affinity is also electronegative, and another kind of material discharges electronics and positively charged.When wall, pipeline or other metal parts of solid particulate and polymerization reactor collided, the quantity of electric charge of transmission depended on metal and particulate electrical property, exposure level, surfaceness and other factors.Research in the pneumatic transport field shows that the frictional electricity of solid particulate also is responsive for the speed of delivering gas.

The amount of the electric charge that is produced is also to being present in the reactor wall that contacts with solid particulate or lip-deep any pollutent sensitivity of other metal parts.Electrically charged height depends on any resin-coated characteristic that may be present in the reactor internal surface.Generally, when wall (ideally) when scribbling high-resistance polyethylene, reduced generation of static electricity.

Be known that the static activity in the polymerization reactor system can be relevant with the reduction or the interruption (break event) of the polymer buildup of the formation of polymkeric substance skinning and/or reactor and the polymer production that is caused.To the active detection of this static with the fluidized-bed part be confined to reactor usually is discussed, i.e. Chuan tight section, usually more than the distribution plate more than distribution plate distance be the about 3/4 of reactor diameter, or the above reactor diameter of distribution plate 1/4 to 3/4.Yet for the metalloscene catalyst in the gas-phase reaction, the electrostatic probe of conventional previously known usually can not effectively be predicted the reactor interrupt event.In the reaction of metallocene catalyst, conventional electrostatic probe has usually shown very little or has not had static activity (even in skinning event procedure).Specifically, though one or more electrostatic probes have shown static activity (we it is now know that it is the indication of reactor interrupt event) in the entrainment zone of reactor, conventional electrostatic probe has usually shown very little or has not had the static activity.Also known these problems change in the polymer production technological process in time.In embodiments of the invention, before be not used in monitoring static electric charge (measuring) that detects static charge and the ability of in the entrainment zone of reactor, doing like this by electric current/unit surface, make can the employed continuity additives of dynamic adjustments amount.That is to say, according to amount as the active horizontal adjustment continuity additives of static in the reactor assembly that detects by one or more unconventional entrainment zone electrostatic probes.Term static activity, static electrification and static can exchange use here.When the static in discussing entrainment zone is active, also use " carrying static " to represent.

Entrainment zone is defined as the above or following any zone of emulsion zone of reactor assembly.Fluidization enclosure with bubbling bed comprises two districts, a fine and close bubbling phase, and it has it and upper surface stingy or that disperse phase separates.Fine and close bed (on) container portions between surface and the discharge air-flow (to recirculation system) is called as " freeboard of fluidized bed ".Therefore, entrainment zone comprises freeboard of fluidized bed, and the bottom of circulation (recirculation) gas system (comprising pipeline and compressor/water cooler) and reactor is to the top of distribution plate.The static activity of measuring Anywhere in entrainment zone is called as " carrying static " here, like this, with the static activity of measuring by the one or more conventional electrostatic probe in the fluidized-bed difference is arranged.

We it has surprisingly been found that, beginning relevantly in " zero or approximately zero " mensuration static activity (carrying static) level (as above definition) more than and skinning, caking or they in the polymer reaction system on the particle carrying in entrainment zone, is the indication of comparing higher skinning of dependency or interrupt event with the static activity of one or more " routine " electrostatic probe mensuration.In addition, have been found that the carry particulate static activity of monitoring in the entrainment zone provides reactor parameter, amount that thus can the dynamic adjustments continuity additives also obtains optimum level, to reduce or eliminate interrupt event.

If the order of magnitude of the static activity level in the entrainment zone increases in reaction process, the amount of the continuity additives in so can be as further describing the corresponding conditioned reaction device system.

Electrostatic probe

Being described as be in electrostatic probe in the entrainment zone here comprises following one or more: at least one recirculation conduit electrostatic probe; At least one annular disc probe; At least one distribution plate electrostatic probe; Or at least one reactor top electrostatic probe, the latter be outside 1/4 to the 3/4 reactor diameter height more than the distribution plate of these one or more conventional probes or more than.These probes can be carried static secretly separately or with the mensuration of coming together from one or more other probes in above-mentioned each group.Fig. 1 shows some main positions of using described instrument in embodiments of the invention.These instruments comprise the one or more conventional static detector in fluidized-bed as described herein (" popular response device electrostatic probe ").

Fig. 2 shows an example of popular response device electrostatic probe.These one or more probe assays are as granule impact result's (by catalyzer and/or resin) the electric current that flows through from tips of probes.The estimated value of the charge transfer that takes place on reactor wall generally is provided from the mensuration electric current (per unit area) of tips of probes.Tips of probes has been represented effectively and has been equipped the part that instrument is used to measure the reactor wall of flow of charge.The tips of probes of these detectors and all other probes as herein described can be made by any conductor, comprise carbon steel, iron, and stainless steel, titanium, platinum, nickel,

Alloy, copper, aluminium, perhaps they can be bimetal (wherein a kind of metal have formed core, and another kind of metal has formed epidermis or top layer).At US6, provide further specifying of conventional electrostatic probe in 008,662.

Exemplary currents level with popular response device probe assay is ± 0.1-10, or ± 0.1-8, or ± 0.1-6, or ± 0.1-4, or ± 0.1-2 receives ampere/cm ²The same with all current measurement values as herein described, these values usually also are the mean value in the time period as herein described, also have, and they can represent root-mean-square value (RMS), in this case, they all be on the occasion of.Yet the most common is, in the reactor that adopts metalloscene catalyst, popular response device probe the beginning of skinning incident or mid-term record zero or approximately zero.So-called zero or approximately zero, we are meant value≤± 0.5 of the probe in conventional static reactor probe and the entrainment zone, or≤± 0.3, or≤± 0.1, or≤± 0.05, or≤± 0.03, or≤± 0.01, or≤± 0.001 or 0 receive ampere/cm ²For example ,-0.4 observed value be " less than " " ± 0.5 " ,+0.4 observed value is like this equally.

Other place as this paper is pointed, conventional electrostatic probe can write down zero or approximately zero static or electric current (as defined herein), and at least one other electrostatic probe at least one position of entrainment zone can write down static activity or the electric current (under the situation of metalloscene catalyst, conventional electrostatic probe most possibly is zero or approximately zero) that is higher than by conventional electrostatic probe mensuration.In this case, if poor 〉=± 0.1 between electric current of measuring by conventional electrostatic probe and the electric current measured by one or more other (unconventional) electrostatic probes, or 〉=± 0.3, or 〉=± 0.5 receive ampere/cm ²Or higher, take action reduces or eliminates static charge in the detection of one or more entrainment zone probes.This action can be to add at least a continuity additives (or net increase of the amount of at least a continuity additives in reactor), or reduces catalyst charge speed, or reduces gas by speed, or their combination.These action constituted keep carrying static and reactor static zero or approximately zero, reduce or eliminate the means of carrying static and reactor static.

The recirculation conduit electrostatic probe

At least one recirculation conduit electrostatic probe can be positioned at any position of recirculation conduit, i.e. outlet from the import of the recirculation conduit of reactor head to the recirculation conduit of reactor bottom.This comprises that recirculation conduit import from reactor head is to water cooler or compressor (they can spatially exchange each other), between water cooler and compressor, after water cooler or compressor, between the recirculation conduit outlet of water cooler or compressor and reactor bottom.For at least one recirculation conduit electrostatic probe, we have imagined 1,2,3,4,5,6,7,8,9,10 or these more a plurality of recirculation conduit electrostatic probes at one or more positions.

Fig. 3 shows the embodiment of at least one recirculation conduit electrostatic probe.Tips of probes in this embodiment can be carbon steel rod (or other material as described herein), and it can approximately extend to the center of recirculation conduit.In addition, at least one recirculation conduit probe can become any angle or vertical with the recirculation conduit wall with the recirculation conduit wall.In addition, at least one recirculation conduit probe can extend to 0.1-0.9D in the recirculation conduit, or 0.2-0.8D, or 0.3-0.7D, or 0.4-0.6D, or 0.5D, and wherein D is the internal diameter of recirculation conduit.When flowing through probe, some solid particulates clash into this rod and transfer charge when recycle gas and entrained solid particle (resin and/or catalyst/support particle).Electric current from least one recirculation conduit electrostatic probe can be ± 0-50 receives ampere/cm ², or ± 0.01-25, or ± 0.01-20, or ± 0.1-15, or ± 0.1-10, or ± 0.1-7.5, or ± 0.1-5.0, or ± 0.1-2.5, or ± 0.1-1.5, or ± 0.1-1.0 receives ampere/cm ²

The annular disc electrostatic probe

At least one annular disc electrostatic probe can be positioned at any position on the annular disc, or with the annular disc level, described annular disc electrostatic probe is that gas and/or liquid and/or entrained solid particulate materials flow (under high relatively speed) flow through annular opening inlet is provided.The top of probe can protrude through and reaches 0.1-0.9D in the annular opening, or 0.2-0.8D, or 0.3-0.7D, or 0.4-0.6D, or the distance of 0.5D, and wherein D is the internal diameter of annular disc.We have imagined 1,2,3,4,5,6,7,8,9,10 or these more a plurality of annular disc electrostatic probes.Tips of probes must be installed by insulating material, so that prevent electrically contacting between tips of probes and annular metallic surface (and reactor wall).Electric current from least one annular disc electrostatic probe can be ± 0-50 receives ampere/cm ², or ± 0.01-25, or ± 0.01-20, or ± 0.1-15, or ± 0.1-10, or ± 0.1-7.5, or ± 0.1-5.0, or ± 0.1-2.5, or ± 0.1-1.5, or ± 0.1-1.0 receives ampere/cm ²

Bed top electrostatic probe

At least one top electrostatic probe position in reactor can be higher than the upper limit (equaling 3/4 times the distance more than distribution plate of reactor diameter) of conventional electrostatic probe, or be generally equal to 0.8 or 0.9 or 1.0 times distance of reactor diameter and above distance, until the position of the conical part of the vertical wall contact reactor of reactor.We have imagined 1,2,3,4,5,6,7,8,9,10 or more a plurality of beds top electrostatic probe.Electric current from least one top electrostatic probe can be ± 0-50 receives ampere/cm ², or ± 0.01-25, or ± 0.01-20, or ± 0.1-15, or ± 0.1-10, or ± 0.1-7.5, or ± 0.1-5.0, or ± 0.1-2.5, or ± 0.1-1.5, or ± 0.1-1.0 receives ampere/cm ²

The distribution plate electrostatic probe

At least one distribution plate electrostatic probe also is referred to as the distribution plate cap, and the another kind of mode of electrostatic of carrying is measured in representative.At least one distribution plate probe comprises the above metal cap in one or more holes that places distribution plate.These caps and distribution plate insulate, and are connected in rheometer by cable.At least one probe assay since catalyzer and/or resin particulate to the current transfer that impact caused of described one or more metal caps.Distribution plate electrostatic probe (cap) can be made by carbon steel or aforesaid other conductor, to simulate the charge transfer that is taken place on all other (the not assembling instrument) caps on the distribution plate.Ideally, these distribution plate probes (cap) are by making with distribution plate and cap identical materials.That submitted on December 26th, 2002, that on July 8th, 2004 published, title provides and can be used for measuring the additional detail that carries electrostatic distribution plate electrostatic probe for the US of " Static Measurement and Detection in a GasPhase Polyethylene Reactor " discloses 20040132931.We have imagined 1,2,3,4,5,6,7,8,9,10 or these more a plurality of distribution plate electrostatic probes.The electric current that at least one distribution plate probe is measured can be ± 0-50 receives ampere/cm ², or ± 0.01-25, or ± 0.01-20, or ± 0.1-15, or ± 0.1-10, or ± 0.1-7.5, or ± 0.1-5.0, or ± 0.1-2.5, or ± 0.1-1.5, or ± 0.1-1.0 receives ampere/cm ²

Any one of these electrostatic probes on any position of entrainment zone can be with the electrostatic probe of the beginning or the existence of the reactor interrupt event of making decision, or can unite use with one or more on another position at each locational one or more (recirculation conduit, annular disc, bed top and/or distribution plate electrostatic probes), play this decisive roles.Described electrostatic probe can also play a role separately, if promptly at a locational probe opening entry to the static activity, can take action (as following pointed) so by adding continuity additives and reduce or eliminating electric charge, perhaps one or more continuity additives Already under the situation in the reactor (for example, because with the catalyzer feeding), can add other continuity additives by another charging except catalyst charge usually so.

The active mode of static that is used for monitoring reaction device system by as known in the art or electrostatic probe as described herein provide.This electrostatic probe comprises the metal probe top, one or more signal wires, electric connection line (feed-through), and surveying instrument.Tips of probes can comprise cylindrical bar, but can be for example square, rectangle, trilateral or ellipse of any transverse shape.As for material, tips of probes can be any as described herein conductor.As for signal wire, can use any conventional insulated wire.As for electric connection line, can use any suitable wire, as long as it provides the necessary electrical isolation with ground (and reactor wall), and provide required pressure sealing to prevent that high-pressure reactor gas from spilling from reactor.The electric connection line that is fit to can buy from Conax Buffalo Corp. and other supplier there.

As for the reading of monitoring electrostatic probe, can use any instrument or the equipment of the electric current that can measure from the tips of probes to ground.The instrument that is fit to comprises amperometer, picoammeter (highly sensitive amperometer), volt ohm-milliammeter or electrometer.Can also monitor the mensuration electric current by measuring by the voltage that electric current produced indirectly by resistors in series.Electric current is in this case measured by the voltage of measuring by Ohm's law I=V/R, and wherein I is electric current (ampere), and V is that mensuration voltage (volt) and R are resistance (ohm).As at US 6,008, pointed in 662, the value of resistors in series can be 1 ohm to 4 * 10 ¹¹Ohm does not influence the value of the current indication that is obtained basically.

Handle the method for levels of current

Those skilled in the art will appreciate that the method for many processing from the current signal of electrostatic probe can be arranged.These methods comprise simple weighted average, with average 10 milliseconds to 10 hours, or 10 seconds to 10 hours, or 30 seconds to 5 hours, or 1 minute to 1 hour, or 1 minute to 1/2 hour, or 1 minute to 10 minutes time.Scheme in addition or as an alternative, can handle described signal, with rootmean-square (RMS) derivative that the fundamental current signal is provided, the standard deviation of fundamental current signal, the absolute value of fundamental current signal, or average (the adopting above-mentioned mean time) of the absolute value of fundamental current signal.

Continuity additives

When above firm one or more electrostatic probe opening entries of discussing during to the static activity (be defined as respectively and be higher or lower than " zero or approximately zero ") that is higher or lower than zero, should take measures to reduce this level or make the static activity level turn back to zero or approximately zero, we have pointed out that this can prevent, reduces or eliminate the reactor interrupt event.The measure of being considered comprises adds one or more continuity additives.This interpolation can have the effect (if having had certain level) that improves the level of continuity additives in reactor.The total amount that is present in one or more continuity additives in the reactor generally is no more than 250 or 200, or 150, or 125 or 100 or 90 or 80, or 70, or 60, or 50, or 40, or 30,20 or the amount of 10ppm (the weight PPM of the polymkeric substance that will produce) and/or continuity additives be based on the polymkeric substance that will produce weight 0, or greater than 1, or 3, or 5, or 7, or 10, or 12, or 14, or 15, or 17 or 20ppm (representing by a poundage or the kilogram number of unit time usually).Any of these lower limit can make up with any upper limit.The amount of these continuity additives has been considered a kind of, two kinds, three kinds, four kinds or more kinds of continuity additives, one or both or the total amount of multiple continuity additives in reactor will be considered to the disclosed additive that comes from any source more than all.Continuity additives can directly join in the reactor by the feed pipeline of special use, and/or joins in any suitable feedstream, comprises ethylene feed streams, comonomer feedstream, catalyst charge pipeline, or recirculation conduit.If use more than one continuity additives, each can be used as independent feedstream and joins in the reactor, and perhaps any combination as independent feedstream or mixture joins in the reactor.The mode that continuity additives is joined in the reactor is not important, as long as additive fully disperses in fluidized-bed, and their feeding rate (or concentration) is regulated so that minimum mode of carrying electrostatic level as indicated above to be provided.

We imagine, the total amount of above-described continuity additives can comprise the continuity additives from any source, the continuity additives that adds with catalyzer for example, the continuity additives that in the continuity additives pipeline of special use, adds, the continuity additives that in any recycle stock, contains, or their combination.In one embodiment, the continuity additives of a part joined in the reactor before can measuring any static activity as preventive measures, in this case, when being higher than the static activity of " zero or approximately zero " level when one or more electrostatic probes have write down, increasing continuity additives so that record active these the one or more probes of static and turn back to zero or approximately zero.

Also in the scope of embodiment of the present invention be, in catalyst mixture, introduce at least a continuity additives, again this catalyst mixture (containing at least a continuity additives) is injected in the reactor assembly; Scheme in addition or as an alternative, independently at least a continuity additives is incorporated in the reactor assembly via special-purpose continuity additives feed pipe, with catalyst mixture, makes that this at least a continuity additives with enough concentration is incorporated in the reactor to prevent or to eliminate the reactor interrupt event.Can adopt any of these feed schemes or these two kinds.Continuity additives in catalyzer/continuity additives mixture and the continuity additives that adds via independent continuity additives feed pipe can be identical or different.

The definite of best continuity additives feeding rate who is fed into reactor assembly proved by zero or the approximately zero static value of carrying as this paper defined.For example in the stopping reaction device carry the static reading after, if add the continuity additives of additional (promptly higher) amount, if and the one or more electrostatic probes in the entrainment zone of reactor have shown increasing of static reading, this is the qualitative indication that has surpassed best continuity additives level so.In this case, should reduce the level of continuity additives, up to reaching static active stable (as indicated) once more, perhaps the static activity is reduced to approximately zero or return to zero by the metastable static activity readings of one or more electrostatic probes.Therefore, the amount of dynamic adjustments continuity additives is desirable to reach optimum concentration range, and in the scope of embodiment of the present invention.So-called optimum concn is meant significant quantity here.Therefore, at least a continuity additives of significant quantity is to reduce or static charge or the static charge eliminating as measured by one or more electrostatic probe obtain stable amount.Therefore, pointed as this paper, if add too many continuity additives, static charge will reappear; The amount of this continuity additives is considered to outside the significant quantity scope.

Be applicable to that continuity additives of the present invention comprises that one or more are selected from the compound in alkoxylated amines, carboxylate salt, polysulfones, polymerized polyamines and the sulfonic acid class.

Continuity additives can comprise the ethoxylation stearic amine.The ethoxylation stearic amine that can be purchased from ICI and branch thereof can be supplied with trade mark AS990 from the another kind of ethoxylation stearic amine that Witco ChemicalCompany is purchased with trade mark ATMER 163 supplies.

Other continuity additives that is fit to comprises aluminum stearate and aluminium oleate.Also have some other continuity additives that are fit on market, supply with STADIS (these are considered to identical or similar chemical substance) with trade mark OCTASTAT and/or, describe also and can buy in 026,795 from Octel Starreon at US patent No.5.

In another embodiment, continuity additives can be the mixture of above-mentioned two or more continuity additives.This mixture can comprise: alkoxylated amines and carboxylate salt; Or alkoxylated amines and polysulfones; Or alkoxylated amines and polymerized polyamines; Or alkoxylated amines and sulfonic acid class; Or carboxylate salt and polysulfones; Or carboxylate salt and polymerized polyamines; Or carboxylate salt and sulfonic acid class; Or polysulfones and polymerized polyamines; Or polysulfones and sulfonic acid class; Or polymerized polyamines and sulfonic acid class.In addition, we have considered alkoxylated amines, carboxylate salt and polysulfones; Or alkoxylated amines, polymerized polyamines and sulfonic acid class; Or carboxylate salt, polysulfones and polymerized polyamines; Or carboxylate salt, sulfonic acid class and polysulfones; Alkoxylated amines, carboxylate salt and polymerized polyamines; Alkoxylamine, carboxylate salt and sulfonate; Alkoxylamine, polysulfones and sulfonic acid class; Alkoxylamine, polymerized polyamines and polysulfones; Polysulfones, polymerized polyamines and sulfonic acid class; Carboxylate salt, polymerized polyamines and sulfonic acid class.The combination of four kinds or more kinds of these continuity additives also is considered.These compositions can be with 10:90-90:10, or 25:75-75:25, or 40:60-60:40, or the ratio of 50:50 merges, and perhaps under the situation of three kinds of continuity additives, merges with the ratio of 10:10:80-80:10:10 or 10:80:10.The absolute magnitude of these continuity additives as mentioned above.

The other continuity additives that is used for embodiment of the present invention comprises the mixture of following component: the 1-decene-polysulfones that exists with the concentration of the 5-15wt% of mixture, the N-butter-1 that exist with the concentration of the 5-15wt% of mixture, the reaction product of 3-diaminopropanes and Epicholorohydrin, the Witco 1298 Soft Acid that exists with the concentration of the 5-15wt% of mixture, and the hydrocarbon solvent that exists with the concentration of the 60-88wt% of mixture, this mixture can trade mark OCTASTAT3000 (can also obtain as STADI S450) or OCTASTAT 200 (can also as STADIS 425) is purchased from Octel Starreon and branch thereof, and they can have separately and above firm those different percentage of discussing are formed.

If adopt the composition of continuity additives, be present in the reactor whole amounts as mentioned above.

Catalyzer

All polymerizing catalysts that comprise conventional transition-metal catalyst and metalloscene catalyst or their combination are adapted at using in the embodiment of method of the present invention.It is also conceivable that such as AlCl ₃, cobalt, iron, palladium, chromium/chromic oxide or " Philips " catalyzer and so on catalyzer.It below is the non-limiting argumentation that can be used for various polymerizing catalysts of the present invention.

General Definition

As used herein phrase " catalyst system " comprises at least a " catalyst component " and at least a " activator ", perhaps at least a promotor.Catalyst system can also comprise other component, carrier for example, and be not limited to separately or bonded catalyst component and/or activator.Catalyst system can comprise many catalyst components of any arbitrary combination as described herein, and the activator of any arbitrary combination as described herein.

The employed phrase of this paper " catalyst compound " comprises in case suitably activated, polymerization or oligomeric any compound that can catalyzed alkene, this catalyst compound comprises at least one 3-12 family atom, and optional keyed jointing at least one leavings group thereon.

The employed phrase of this paper " leavings group " is meant and can captures from catalyst component by enough activators, therefore forms one or more chemical structure parts of the metal center that is bonded in catalyst component with olefinic polymerization or oligomeric active material.Further activator is described following.

About the periodictable " family " of element, adopt as at CRC HANDBOOK OF CHEMISTRYAND PHYSICS (David R.Lide ed., CRC Press 81 ^StEd.2000) " newly " numbering plan of the periodictable in.

This paper employed " alkyl " comprises the aliphatic series that comprises carbon and hydrogen, ring-type, olefinic, acetylene series and the aromatic group (being alkyl) that lacks a hydrogen." alkylene " lacks two hydrogen.

The employed phrase of this paper " heteroatoms " comprises any atom except carbon and hydrogen that can be bonded in carbon." containing heteroatomic group " is to contain heteroatoms and can contain one or more identical or different heteroatomic alkyl.In one embodiment, containing heteroatomic group is to contain 1-3 alkyl that is selected from the atom in boron, aluminium, silicon, germanium, nitrogen, phosphorus, oxygen and the sulphur.The limiting examples that contains heteroatomic group comprises imines class, amine, oxide compound, phosphine class, ethers, ketone, oxoazolines heterocycle, oxazoline class and thioether class group.

As used herein " heterocycle " is meant to have and comprises 1-3 member ring systems that is selected from the carbon skeleton of the atom in boron, aluminium, silicon, germanium, nitrogen, phosphorus, oxygen and the sulphur, unless heteroatoms (non-carbon atom) is illustrated.

This paper employed " alkyl carboxylic acid root ", " aryl carboxylic acid root " and " alkaryl carboxylate radical " are respectively alkyl, aryl and the alkaryls that has carboxyl in any position.Example comprises C ₆H ₅CH ₂C (O) O ^-, CH ₃C (O) O ^-Deng.

Term as used herein " replacement " is meant that the group after this term has at least one structure division of the one or more hydrogen that replace any position, this structure division be selected from such as halogen radical (Cl especially, F, Br), hydroxyl, carbonyl, carboxyl, amido, phosphino-, alkoxyl group, phenyl, naphthyl, C ₁-C ₁₀Alkyl, C ₂-C ₁₀The group of alkenyl and their combination and so on.The alkyl that replaces and the example of aryl include but not limited to acyl group, alkylamino, alkoxyl group; aryloxy, alkylthio, dialkyl amido; alkoxy carbonyl; aryloxycarbonyl, formamyl, alkyl-carbamoyl and dialkyl amido formyl radical; acyloxy; acyl amino, arylamino, and their combination.

Unless otherwise prescribed, any embodiment of the present invention here be not limited to as following each describe and embodiment in the oxidation state of defined atoms metal " M ".

Metallocene catalyst components

The catalyst system that can be used for embodiment of the present invention comprises at least a metallocene catalyst components as described herein.For example, metallocene catalyst compound is at 1﹠amp; 2METALLOCENE-BASED POLYOLEFINS (John Scheirs ﹠amp; W.Kaminsky eds., John Wiley ﹠amp; Sons, Ltd.2000); G.G.Hlatky, 181 COORDINATIONCHEM.REV.243-296 (1999) and especially for the metallocene catalyst compound of synthesizing polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000) by describe, in general terms.Comprise and to have one or more Cp parts of being bonded at least one 3-12 family atoms metal (cyclopentadienyl and with the part of cyclopentadienyl isomorphism (isolobal)) and " half is sandwich " and " sandwich entirely " compound of being bonded in one or more leavings groups of this at least one atoms metal as described metallocene catalyst compound in this article.Hereinafter, these compounds are called as " metallocenes " or " metallocene catalyst components ".In one embodiment, metallocene catalyst components supports on solid support material, and can with or do not support with another catalyst component.

The Cp part is one or more rings or member ring systems, and its at least a portion comprises the system of π keyed jointing, as cycloalkadienyl part and heterocyclic analogs.This ring or member ring systems generally include the atom that is selected from the 13-16 family atom, and the atom of perhaps forming the Cp part is selected from carbon, nitrogen, and oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium and their combination, wherein carbon accounts at least 50% of annular atoms.Perhaps, the Cp part be selected from replace and unsubstituted cyclopentadienyl ligands and with the part of cyclopentadienyl isomorphism, their limiting examples comprises cyclopentadienyl, indenyl, fluorenyl and other structure.The further limiting examples of these parts comprises cyclopentadienyl, cyclopentano phenanthryl, indenyl, benzo indenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraene base, cyclopentano ring dodecylene, phenanthridinyl, 3,4-benzo fluorenyl, 9-phenyl fluorenyl, 8-H-cyclopentano acenaphthenyl (acenaphthylenyl), 7H-dibenzo fluorenyl, indeno [1,2-9] anthrene, the thieno-indenyl, thieno-fluorenyl, their hydrogenation modification (for example 4,5,6,7-tetrahydro indenyl, or " H ₄Ind "), their replacement modification, and their heterocycle modification.

The catalyst component that contains 15 family's atoms

One aspect of the present invention comprise separately or the catalyst component that uses so-called " containing 15 family's atoms " with metallocenes or other olefin polymerization catalyst components as the ideal catalyst component.Usually, " catalyst component that contains 15 family's atoms " mentioned here comprises 3-12 family metal complexes, and wherein metal is the 2-8 coordinate, and these one or more coordination structures partly comprise at least two 15 family's atoms and 4 15 family's atoms at the most.In one embodiment, the catalyst component that contains 15 family's atoms is the title complex of 4 family's metals and 1-4 part, makes that 4 family's metals are at least 2 coordinate, and these one or more coordination structures partly comprise at least two nitrogen.The compound that representativeness contains 15 family's atoms for example is disclosed in WO 99/01460; EP A1 0 893454; EP A1 0,894 005; US 5,318, and 935; US 5,889,128, US6, and 333,389B2 and US 6,271 are among the 325B1.

In one embodiment, the catalyst component that contains 15 family's atoms that can be used for embodiment of the present invention comprises the 4 families imino--phenol title complex of the olefin polymerizating activity with any degree, two (amino) title complexs of 4 families and 4 family's pyridyl-amino title complex.

Activator

Term as used herein " activator " is defined as supporting or non-any compound or the combination of compounds that supports, they for example can activate single site catalysis immunomodulator compounds (metallocenes for example contains the catalyzer of 15 family's atoms) by produced cationic substance by catalyst component.Usually, this relates to from the metal center of catalyst component and captures at least one leavings group (the X group above general formula/structural formula) there.Therefore the catalyst component of embodiment of the present invention uses this type of activator activation, is used for olefinic polymerization.The example of these activators comprises Lewis acid such as ring-type or oligomeric poly-(oxidation alkyl aluminium) and so-called non-coordination activator (" NCA ") (perhaps, " ionization activator " or " stoichiometry activator (stoichiometricactivator) "), maybe the neutral metal metallocene catalyst components can be converted into cationic any other compound of the metallocenes with olefin polymerizating activity.

Within the scope of the present invention be, use Lewis acid such as aikyiaiurnirsoxan beta (for example " MAO "), modified alumoxane (for example " TIBAO "), with alkylaluminium cpd as activator, and/or use ionization activator (neutrality or ion) for example four (pentafluorophenyl group) boron, three (normal-butyl) ammoniums and/or three perfluorophenyl boron metalloid precursors, to activate metallocenes as herein described.MAO and other aluminum-based activators are known in the art.The ionization activator is known in the art, for example by Eugene You-Xian Chen and Tobin J.Marks, at Cocatalystsfor Metal-Catalyzed Olefin Polymerization:Activators, Activation Processes carried out description among and Structure-Activity Relationships100 (4) the CHEMICAL REVIEWS 1391-1434 (2000).As GregoryG.Hlatky, described in Heterogeneous Single-Site Catalysts for OlefinPolymerization 100 (4) the CHEMICAL REVIEWS 1347-1374 (2000), described activator can associate with carrier or combine, or this is with catalyst component (for example metallocenes), or separates with catalyst component and to carry out.

The Ziegler-Natta catalyst component

Catalyst composition comprises the catalyst component that belongs to (or comprising) non-metallocene compounds.In one embodiment, this catalyst component comprises the Ziegler-Natta catalyst compound, for example in ZIEGLER CATALYSTS 363-386 (eds., Springer-Verlag 1995 for G.Fink, R.Mulhaupt and H.H.Brintzinger); Or EP 103 120; EP 102503; EP 0 231 102; EP 0 703 246; RE 33,683; US 4,302, and 565; US5,518,973; US 5,525, and 678; US 5,288, and 933; US 5,290, and 745; US 5,093,415 and US 6,562,905 in disclosed compound.The example of this type of catalyzer comprises that those comprise the catalyzer of following component: 4,5 or 6 group 4 transition metal oxide compounds, alkoxide and halogenide, the perhaps oxide compound of titanium, zirconium or vanadium, alkoxide and halogenide; Choose wantonly and magnesium compound, interior and/or external electronic donor (alcohol, ether, siloxanes etc.), aluminum alkyls or boron alkyl and alkyl halide and inorganic oxide carrier combination.

The transition-metal catalyst of general type is those traditional Ziegler-Natta catalysts well known in the art.The example of the transition-metal catalyst of general type is at US patent Nos.4, states in 115,639,4,077,904,4,482,687,4,564,605,4,721,763,4,879,359 and 4,960,741.The transition metal catalyst compound of the general type that can use in the present invention comprises the 3-17 family of the periodic table of elements, or 4-12 family, or the transistion metal compound of 4-6 family.

The transition-metal catalyst of these general types can represent that wherein M is a 3-17 family metal, or 4-6 family metal, or 4 family's metals, or titanium with formula M Rx; R is halogen or-oxyl; And x is the valency of metal M.The example of R comprises alkoxyl group, phenoxy group, bromide anion, chlorion and fluorion.Wherein M is that the example of transition-metal catalyst of the general type of titanium comprises TiCl ₄, TiBr ₄, Ti (OC ₂H ₅) ₃Cl, Ti (OC ₂H ₅) Cl ₃, Ti (OC ₄H ₉), Cl, Ti (OC ₃H ₇) ₂Cl ₂, Ti (OC ₂H ₅) ₂Br ₂, TiCl ₃-1/3AlCl ₃And Ti (OC ₁₂H ₂₅) Cl ₃

Can be used for embodiment of the present invention based on the transition metal catalyst compound of the general type of magnesium/titanium electron donor(ED) title complex for example at US patent Nos.4, state in 302,565 and 4,302,566.Considered that also by Mg/Ti/Cl/THF deutero-catalyzer, they are that those ordinarily skilled in the art are known.An example for preparing the general method of this catalyzer may further comprise the steps: with TiCl ₄Be dissolved among the THF, use Mg that this compound is reduced to TiCl ₃, add MgCl ₂, remove again and desolvate.

The cocatalyst compound of general type that is used for the transition metal catalyst compound of above-mentioned general type can be used formula M ³M ⁴ _vX ² _cR ³ _B-cExpression, wherein M ³Be the 1-3 of the periodic table of elements and the metal of 12-13 family; M ⁴It is 1 family's metal of the periodic table of elements; V is the numerical value of 0-1; Each X ²It is any halogen; C is the numerical value of 0-3; Each R ³Be univalence hydrocarbyl or hydrogen; B is the numerical value of 1-4; Wherein b-c is at least 1.The organo-metallic cocatalyst compound of other general type that is used for the transition-metal catalyst of above-mentioned general type has formula M ³R ³ _k, M wherein ³Be IA, IIA, IIB or IIIA family metal, lithium for example, sodium, beryllium, barium, boron, aluminium, zinc, cadmium and gallium; K equals 1,2 or 3, depends on M ³Valency, this valency and then depend on M usually ³Affiliated specific family; And each R ³It can be any monoradical that comprises alkyl and contain the alkyl of 13-16 family element such as fluorine, aluminium or oxygen or their combination.

Polymerization

Polymerization can be adopted above catalyzer and the monomer that is selected from ethene and one or more alpha-olefins of selecting from 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene or 1-decene carries out.

In order to understand the present invention better, provide and in enforcement of the present invention, carry out the relevant following examples of actual tests:

Embodiment

Polyreaction as herein described is carried out in the continuous pilot scale gas-phase fluidized-bed reactor of 4.0 meters of 0.57 meter of internal diameter and the height of bed.This fluidized-bed is made up of polymer beads.The gas raw material stream of ethene and hydrogen mixes in the hybrid tee device with the liquid copolymeric monomer, and is incorporated into below reactor beds in the recycle gas pipeline.Adopt hexene as comonomer.The flow separately of control ethene, hydrogen and comonomer is to be maintained fixed the composition target.The control ethylene concentration is to keep the constant ethylene partial pressure.Control hydrogen is to keep constant hydrogen and ethylene molar ratio.Measure the concentration of all gas to guarantee the composition of relative constant recirculated air by on-line gas chromatography.

Use the nitrogen of purifying solid catalyst directly to be injected in the fluidized-bed as carrier.The speed of regulating it is to keep the constant throughput rate.Replenish raw material and recycle gas Continuous Flow and cross the bed that reaction zone reacts the growing polymer particulate and remain on fluidized state by allowing.Use the superficial gas velocity of 0.6-0.9 meter per second to reach this purpose.Reactor is worked under the total pressure of 2170kPa.In order to keep the constant temperature of reactor, the temperature that raises or reduce recycle gas continuously is to adapt to any change of the heat production speed that causes owing to polymerization.

Make fluidized-bed remain on constant altitude (4.0 meters) by a part of discharging bed with the speed that equals granular product formation speed.Product forms speed (polymer production rate) in the scope of 50-70kg/h.Product semi-continuously is discharged into via series of valves in the chamber of fixed volume, returns simultaneously to be discharged in the reactor.This makes can discharge product highly effectively, simultaneously with most unreacted gas re-circulation in reactor.This product is purged, also use shallow bid humidifying nitrogen steam treatment with the hydro carbons that removes deentrainment, with the residual catalyst of any trace of passivation.

Fig. 1 is the synoptic diagram of the approximate location of pilot scale fluidized-bed reactor and electrostatic measurement instrument.

Reading from electrostatic probe is measured with the form of electric current.This electric current is measured by Keithley6517A type electrometer (with current mode work).The data that adopt the scanning card in the 6517A type electrometer to collect a plurality of probes simultaneously.The data of each probe are collected with the speed of 125 reading/seconds, per 6 seconds report mean value.Scheme is connected in special-purpose Keithley 485 type picoammeter with described probe as an alternative.Under this alternative case, each electrostatic probe is connected in this strapping table continuously, and this shows to report per 5 seconds " point " or the momentary value of electric current.Data record in the computer daily record of two types rheometer report, and be used to produce curve shown in Fig. 4-7.

Fig. 4 shows on the pilot scale Gas-phase reactor by Univation Technologies, the vault skinning incident of the metalloscene catalyst XCAT EZ 100 that LLC supplies on market.Trace line (trace) six of the top of this figure and show top layer thermocouple readings (wall temperature) in the vault.As known in the art, skinning (with vault skinning in this case) is represented with top layer thermocouple readings increase fast (or spike).Before vault skinning incident, recirculation conduit static reading has shown rapid rising, descends suddenly subsequently.Conveying (recirculation) the pipeline electrostatic of measuring descends and is considered to the result that descends from the solid speed that this reactor migrates out.As if solid transfer speed descend consistent with the formation of vault skinning.

Fig. 5 shows 4 continuous vault skinning incidents using XCAT EZ 100 metalloscene catalysts on the pilot scale Gas-phase reactor.Trace line six of this figure top and show top layer thermocouple readings in the vault.Corresponding scale shows on the right.The vault skinning is represented by the quick rising (or spike) of top layer thermocouple readings.Each of four incidents has formed size to be enough to stop up the product discharge outlet and to disturb fluidizing vault skinning.In each of four incidents, operator have to close down reactor and clean.

Recirculation conduit carries the static reading and traces line with the bottom among Fig. 5 and represent.Corresponding scale on the left shows.Before each vault skinning incident, noticed that the recirculation conduit electrostatic sharply raises.In first, third and fourth incident, recirculation conduit static has reached 200 skins peace.In second incident, recirculation conduit static peak has reached 95 skins peace.

Fig. 6 shows the identical vault skinning incident of Fig. 5, and the reading that has wherein increased the distribution plate electrostatic probe is used for comparison.As can be seen from the figure, before vault skinning incident, the distribution plate electrostatic probe has shown some responses, but this response is not remarkable, and is inconsistent.Because the distribution plate probe is carried the particulate contact secretly with identical, so we expect that they can show the response that equates (with proportional) with the recirculation conduit probe.The reason of this difference is unknown.

Fig. 7 has shown the reactor wall skinning incident of metalloscene catalyst XCAT HP 100 catalyzer, and this catalyzer is by Univation Technologies, and LLC supplies on market.In this case, before the skinning incident, observed the remarkable response of two distribution plate probes.

Fig. 7 also provides the fabulous explanation for our previously described problems of measurement, and promptly popular response device electrostatic probe did not provide significant indication before the skinning incident of using metalloscene catalyst.As being traced shown in the line by the reactor among this figure, in (or during) before the wall skinning incident, popular response device electrostatic probe is response not.

Fig. 8 shows the wall skinning data of Fig. 7, has wherein increased recirculation conduit and has carried static and be used for comparison.As can be seen from this figure, the recirculation conduit probe did not provide significant response before wall skinning incident.Occur in after the wall skinning forms from unique remarkable response of this probe.This indication should be monitored all probes that are present in the reactor assembly, because some probes may not record static, and other probe may record static, thereby can control by using continuity additives.

Described experimental data provides some important and unpredictable consequences: recirculation conduit carries electrostatic probe and provided significant response before the vault skinning incident of using metalloscene catalyst.Described distribution plate probe does not obviously provide the indication in advance of vault skinning.

On the contrary, under the situation of wall skinning, the distribution plate probe provided significant response before the wall skinning incident of using metalloscene catalyst, but the recirculation conduit probe does not obviously have.Though these results are opposite with the discovery of vault skinning, the present invention obviously provides for the vault that uses metalloscene catalyst and the solution of wall skinning problem.Measure on recirculation conduit and these two positions of distribution plate (or equivalent) and carry static, these observed values are used in combination with electrostatic control means to keep carrying static in approximately zero level.

In order to determine to carry effective control mode that static remains on about zero level, to testing as the solution in hexane or as the multiple continuity additives of the solids slurry in mineral oil.Solids slurry is used for insoluble component (aluminum stearate), and hexane solution is used for aluminium oleate and is purchased product with trade mark OCTASTAT 3000 and OCATSTAT 2000 by what Associated OctelCompany sold.Aluminium oleate solution is by 0.40% prepared at concentrations; OCTASTAT 2000 and 3000 strength of solution are 0.53wt%.These solution use useful range to be fed into reaction zone as the positive-displacement pump of 100-1200cc/hr.The aluminum stearate slurry prepares by the solid aluminum stearate being joined in the mineral oil that outgased 24 hours with nitrogen under 80-100 ℉.The gained slurry concentration is 5.66wt%.Adopt effective pump of 1-100cc/hr to take out scope, this slurry is fed into reaction zone.Also adopt the flushing thing of iso-pentane as the reactor feed pipeline.

The data indication of pilot scale polymerization reactor, the vault of fluidized-bed reactor and the skinning of hypomere can be controlled and alleviate to the independent interpolation of several additives and independent control simultaneously.Many continuity additives are insoluble relatively, so as mentioned above, they are as the slurry feeding in the mineral oil.The solubility material is dissolved in the hexane, is fed directly in the reactor again.

Test following compounds with XCAT HP 200 and XCAT EZ 100 metallocene catalyst systems:

Aluminium oleate (solution)

Aluminum stearate (slurry)

OCTASTAT 3000 (solution)

OCTASTAT 2000 (solution)

AS-990 (slurry)

ATMER 163 (solution)

Carry out two campaigns, one with XCAT HP 200 metalloscene catalysts, and another is with XCAT EZ 100 metalloscene catalysts.XCAT HP 200 metalloscene catalyst testing sequences by adopt catalyzer and aluminium distearate (based on catalyst weight 3%) the operation of dried mixed thing begin.Start the additive charging then, and press the system operation reactor.Then described catalyzer is switched to a kind of situation (being called " simple catalyzer ") that does not wherein have aluminium distearate, suppose not have the operability problem, will join in the reactor by additive simultaneously.Via independent continuity additives feed pipe, the feeding rate of additive is increased to about 20ppm (weight) stage by stage.Final step is zero when additive flow is decreased to simple catalyzer.XCAT EZ 100 metalloscene catalysts tests is carried out in evaluation is intended for use in the cut-and-try process of operability of catalyzer of industrial test.In this case, respond cold top layer thermocouple readings (negative value that promptly departs from normal temps) and add AS-990, so that carry out operate continuously with XCAT EZ 100 metalloscene catalysts.The additive that produces positive result is:

Aluminum stearate

AS-990

Aluminium oleate

OCTASTAT?2000

Several important discoveries in these processs of the test, have been observed.When using simple catalyzer, when not adding continuity additives separately, produced cold skin temperature reading.In some cases, these values are gradual to become even worse, self reverses suddenly and causes the skinning incident up to them.With the catalyzer/continuity additives of blend, also observed the higher electrostatic level that carries.By adding the continuity additives of higher level, by adding continuity additives (separating) separately, reduced and carried static usually with the blend of catalyzer and continuity additives.That increases carries electrostatic level corresponding to the reactor static level that increases.When the continuity additives flow increases, carry static and reduce.Finally, two skinning incidents increase to feature suddenly to carry the gradual reduction of electrostatic and to carry static subsequently.Adopt the operation of " merely " catalyzer to facilitate these skinning incidents.At this moment, the top layer thermopair having taken place departs from and skinning.As if though the cutter reason is not clear really for this phenomenon, catalyzer attracted on the wall, as being confirmed by carrying static decline.When the generation skin temperature departed from, catalyzer obviously is released and carries static to be increased suddenly.

In the process of the test of multiple continuity additives and the vault of fluid bedreactors estimate.When moving, always there is the vault skinning with catalyzer/continuity additives blend.When improving additive level (generally by independent feed pipe), vault is by gradual cleaning, till it is cleared up the bare metal wall fully.For aluminum stearate, this need be based on the total concn of the 10-15ppm by weight (ppmw) of throughput rate.When with aluminum stearate and catalyzer blend, the productivity restraining factors with the concentration limit of stearate to 6ppm (weight), (this is a level roughly by the percentage of blend, but at this more than level, blend becomes and is difficult to handle, and has therefore proposed physical constraints under the situation of now material and feeding device).More highly active metalloscene catalyst has caused even lower level, promptly comprises 3-4ppmw in blend at most, and having proved needs to add separately this additive.

In the pilot plant polyreaction, test the interference that has been subjected to vault skinning incident with XCAT EZ 100 metalloscene catalysts.Yet the present invention uses the example of continuity additives AS-990 to eliminate cold skin temperature reading, and has eliminated skinning.For example, the slurry of AS-990 in mineral oil is being fed in the reactor when eliminating the cold skin temperature reading in distribution plate and the expanding section, steadily carrying out operation in 10 days and occur without any operational problem.The average approximately 10-30ppm of AS-990 level (from additional charging) in the bed (heavy) based on bed.Attempt to have caused skin temperature to depart from without the test of AS-990.

Fig. 9 shows the data of pilot plant polyreaction in enforcement of the present invention.Data have covered 13 days time.

Each lines at curve top are the skin temperatures of reactor.Show that the lower dotted line that step changes is the flow of continuity additives.The hand-kept flow, this flow changes in the 0-20ppm scope.Point 1 shows when testing simple catalyzer the top layer Temperature Influence, and it has shown the formation of cold skin temperature reading.When increasing the aluminium oleate flow, cold skin temperature reading is eliminated.The further increase of flow causes and forms cold skin temperature reading once more.This proves that this additive has best level.

Point 2 shows the result who cuts off the aluminium oleate inflow and move with simple catalyzer.This proof reduces this additive and has the effect different with increasing this additive-do not have cold skin temperature reading, but skin temperature is offset.This need to have confirmed the additive of optimum level.In a word, be very stable with the test of aluminium distearate, do not find cold skin temperature skew.At point 3 places, the catalyzer of being introduced is switched to simple catalyzer, this has caused forming once more cold skin temperature, but does not have positive skin temperature skew.

Point 4 shows the result of OCTASTAT 2000.This additive is similar to aluminium oleate, has optimum level.In case the flow of continuity additives increases too many, begins to form cold skin temperature.

The curve of Figure 10 is corresponding to the curve among Fig. 9, but in this case, shows three kinds of different electrostatic measurement results.The top that is labeled as reactor static 1 is to use the curve of the reactor static that current probe measures by line, and the middle part curve that is labeled as reactor static 2 is to use the curve of the reactor static of voltage probe, and bottom curve is to carry the electrostatic curve.Carrying static measures by absolute value.Dotted line is the flow of aforesaid continuity additives.

Carry static and during the cold skin temperature at point 1,3 and 4 places forms, descend, though lower in the degree at point 3 places.The point of these band circles shows the interpolation of the blend catalyzer that contains aluminium distearate.In Fig. 9 all other the time, the simple catalyzer of feeding.This proof when the simple catalyzer of feeding only, with the simple catalyzer of feeding and independently simultaneously add continuity additives and compare, is carried static and is increased.

Figure 11 and 12 shows and above those similar curves, but uses OCTASTAT

In Figure 11 and 12, point 1 has formed low carry static and cold skin temperature corresponding to the concentration (total amount in the reactor) of the OCTASTAT 3000 of about 5ppm (weight).Yet when increasing the flow (more than the 5ppm) of OCTASTAT 3000, cold skin temperature disappears, and this proves once more needs best additive level (additive capacity is shown in broken lines).In Figure 11 and 12, at point 2 places, reactor is tested with the OCATSTAT3000 of simple catalyzer and about 41ppm concentration.Stopping OCTASTAT then flows into.Begin immediately to form cold skin temperature, and carry static simultaneously and begin to reduce.Opposite with many other continuity additives, this effect has taken place immediately and not hysteresis aspect cold skin temperature formation.

Figure 11 and 12 proofs, reactor (conventional electrostatic probe) static do not resemble carries the easy and cold skin temperature formation of electrostatic measurement result and is associated.Though reactor static has shown some little variations that change corresponding to reactor condition, reactor static change do not resemble carry static change greatly.In addition, this has proved how gradual cold skin temperature (if staying the long time) can change positive skin temperature skew into.And this proof is carried static and is reduced with cold skin temperature, and until reaching critical level, when this critical level, it begins to increase fast, follows big skew by skin temperature, and this need close down reactor.

Though with reference to particular the present invention has been described, those of ordinary skills are clear, and the present invention itself provides the variation that need not illustrate here.For this reason, should only determine true scope of the present invention so with reference to appended claims.

Claims (12)

1, to prevent or to reverse at least a continuity additives is incorporated into method in the reactor assembly by the amount of the skinning of the polymkeric substance that polyreaction was produced of at least a alkene, wherein this polyreaction is carried out in reactor assembly, this reactor assembly comprises fluidized-bed reactor, entrainment zone, be used to introduce the catalyzer feeding device of the catalyst system that can produce polymkeric substance, at least one is used for introducing independently with catalyst mixture the continuity additives feeding device of at least a continuity additives, be used for monitoring the device of the static activity level of entrainment zone, this method comprises:

(a) allowing this at least a alkene tie up in the fluidized-bed reactor with catalyst body contacts under polymerizing condition;

(b) before polyreaction begins, during or any time afterwards should be incorporated in the reactor assembly by at least a continuity additives;

(c) the static activity level in the monitoring entrainment zone; And

(d) regulate the amount be incorporated into this at least a continuity additives in the reactor assembly, so that the static activity level in the entrainment zone is remained on 0 or near 0;

Wherein this catalyst system comprises metallocenes or conventional transition-metal catalyst; This at least a continuity additives comprises that one or more are selected from the compound in alkoxylated amines, carboxylate salt, polysulfones, polymerized polyamines, sulfonic acid class or their combination; And

The wherein said device that is used for measuring the static activity level of entrainment zone comprises one or more at least one recirculation conduit electrostatic probe, at least one annular disc electrostatic probe, at least one distribution plate electrostatic probe or at least one the reactor top electrostatic probe.

2, the method for claim 1, wherein this method comprises gas phase process.

3, method as claimed in claim 2, wherein continuous production polymkeric substance.

4, method as claimed in claim 3, wherein this monomer comprises ethene or ethene and one or more alpha-olefins.

5, the method for claim 1, wherein this at least a continuity additives comprises the ethoxylation stearylamine.

6, the method for claim 1, wherein this at least a continuity additives comprises aluminum stearate.

7, the method for claim 1, wherein this at least a continuity additives comprises aluminium oleate.

8, the method for claim 1, wherein this at least a continuity additives comprises the mixture of following component: the 1-decene-polysulfones that exists with the concentration of the 5-15wt% of this mixture, the N-butter-1 that exist with the concentration of the 5-15wt% of this mixture, the reaction product of 3-diaminopropanes and Epicholorohydrin, the Witco 1298 Soft Acid that exists with the concentration of the 5-15wt% of this mixture, and the hydrocarbon solvent that exists with the concentration of the 60-88wt% of this mixture; Each component concentration sum is 100wt% in the described mixture.

9, the method for claim 1, its discontinuous is introduced this at least a continuity additives.

10, the method for claim 1, wherein this at least a continuity additives is introduced as the slurry in hydrocarbon liquid or as the solution in hydrocarbon liquid.

11, the method for claim 1, wherein this at least a continuity additives also is present in via the catalyst charge device and is incorporated in the catalyst mixture in the reactor assembly.

12, the method for claim 1, wherein the amount of this at least a continuity additives in fluidized-bed reactor remains on the concentration of 1-50ppm, is benchmark in the weight of the polymkeric substance produced in fluidized-bed reactor.

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