CN1917949A - Method and apparatus for preparing and supplying catalyst slurry to a polymerisation reactor - Google Patents

Method and apparatus for preparing and supplying catalyst slurry to a polymerisation reactor Download PDF

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CN1917949A
CN1917949A CNA2005800049125A CN200580004912A CN1917949A CN 1917949 A CN1917949 A CN 1917949A CN A2005800049125 A CNA2005800049125 A CN A2005800049125A CN 200580004912 A CN200580004912 A CN 200580004912A CN 1917949 A CN1917949 A CN 1917949A
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catalyst
reactor
pipeline
slurry
catalyst slurry
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路易斯·福阿吉
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Total Petrochemicals Research Feluy SA
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Total Petrochemicals Research Feluy SA
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Abstract

The present invention relates to an apparatus for preparing and supplying catalyst to an ethylene slurry loop polymerisation reactor and to an apparatus for controlling the injection of catalyst slurry in a polymerization reactor wherein polyethylene is prepared. The present invention a Iso relates to a method for optimising catalyst supply to a polymerisation reactor. The diluted catalyst is transferred to the reactor (1) using a membrane pump (5) controllable in function of the concentration of a reactant in said reactor (1).

Description

The method and apparatus that is used to prepare catalyst slurry and catalyst slurry is supplied to polymer reactor
Technical field
The present invention relates to catalytic reaction.First aspect the present invention relates to the device that is used to prepare catalyst slurry and polymer reactor is supplied to polymer reactor.The invention still further relates to the device that is used to control to polymer reactor charging catalyst.On the other hand, the present invention relates to be used to optimize the method that is supplied to the polymer reactor catalyst.On the other hand, the present invention relates to be used to control method to polymer reactor charging catalyst.
Background technology
Polyethylene (PE) is by polymerising ethylene (CH 2=CH 2) monomer and optional senior 1-alkene such as 1-butylene, 1-hexene, 1-octene or 1-decene synthesize.Because polyethylene cheapness, safety, to most of ambient stables and be easy to process, so polyethylene polymer is applied to many fields.According to synthetic method, polyethylene can be divided into several types such as LDPE (low density polyethylene (LDPE)), LLDPE (LLDPE) and HDPE (high density polyethylene (HDPE)) usually.Various polyethylene have different character and characteristic.
Know that the polymerization of alkene such as ethene especially by the polymerization of gas phase polymerization process, relates to by means of catalyst and by the optional co-catalyst whether catalyst system therefor decision needs and makes the olefinic monomer polymerization.The catalyst that is applicable to polyolefin prepared, especially polyethene preparation comprises chromium-type catalyst (chromium-type catalyst), Ziegler-Natta catalyst and metallocene catalyst.
Well-known polymerisation is very responsive for the amount of catalyst system therefor.Because catalyst unexpectedly or uncontrollably can cause runaway reaction (runaway reaction) in the injecting reactor, so the control catalyst is important to the mobile of reactor.Yet, with one of subject matter of the method for catalyst slurry injecting reactor, be to be difficult to control the amount of catalyst and the flow velocity of institute's injecting catalyst in the prior art.
According to the catalyst charge system of prior art, the catalyst of conc forms (for example, directly irritating (mud pot) from slurry) or the catalyst of dilute form are provided to polymerisation.
Be to control catalyst fully with catalyst slurry to reactor feed speed from the disadvantage that storage container is fed directly to reactor.And, directly to supply under the situation of (concentrating) catalyst relating to reactor, catalyst can be rinsed (flushed) fully in reactor, at this moment produced problem in Preparation of Catalyst.The not controlled like this catalyst supply runaway reaction in the device that can induce reaction.
And, directly providing under the situation of the catalyst in the oil suspension to reactor, employed pump (normally progressive cavity pump (progressive cavity pump)) is the amount of the catalyst in (dose) catalyst flow and the injecting reactor quantitatively.And such system needs the conversion catalyst injection system, all the catalyst of new lot will be connected to reactor with to its charging at every turn.Therefore, above-mentioned injection system can not provide best and reliable rate of catalyst flow control.
The system of several catalyst slurries that comprise the preparation catalyst slurry and will dilute to the polymerisation supply disclosed.Usually, be the preparation catalyst slurry, the solid granular catalyst of drying and the mixture of diluent are distributed in the catalyst stores container to mix fully.Then, under condition of high voltage, typically these catalyst slurries are directly transferred in the polymerization container usually, to contact with monomer reactant.
The method and apparatus that GB 838,395 relates to, be used for preparation at the slurry of the solid catalyst of hydrocarbon diluent (hydrocarbondiluent) to be used for chemical reaction.This method comprises the catalyst concentration slurry of preparation in hydrocarbon diluent and makes described concentrated catalyst slurry and other mixing diluents, and described mixture is introduced reaction zone.According to this method, before this slurry is introduced described reaction zone, the certain dielectric constant of METHOD FOR CONTINUOUS DETERMINATION slurry (specifc inductive capacity), its dielectric constant is by catalyst concentration decision in this slurry.
US 3,726, and 845 disclose a kind of system, and wherein catalyst slurry prepares in container, after this, by the pipeline that is equipped with pump it are pumped to polymer reactor.By catalyst is flowed selected some seconds to polymer reactor via pipeline, diluent is flowed selected some seconds to polymer reactor via pipeline, and make this catalyst slurry and the diluent that result from the container alternately be fed to polymer reactor via described pipeline.
WO 2004/0264455 discloses a kind of catalyst slurry feeding system, wherein forms the catalyst slurry of dilution in blending tank, and it is delivered to storage tank, wherein before catalyst slurry is supplied to polymer reactor, it is kept diluted state.By means of the pipeline that has valve catalyst slurry is fed to the storage tank from blending tank.Blending tank can be than storage tank position height, so catalyst slurry flows into storage tank by gravity from blending tank at least in part, avoids thus needing pump between blending tank and storage tank.Alternatively,, need not pump and difference in height, catalyst slurry is moved between tank body by keeping the pressure reduction between blending tank and the storage tank.
US 5,098, and 667 disclose a kind of catalyst supply system, and it comprises via the pipeline that comprises the valve system that is used to regulate conveying, the catalyst that concentrates is transferred to cut-back tank from slurry pot.By means of pipeline, the slurry that dilutes is supplied to polymer reactor continuously.In described method, the flow velocity of control dilution slurry is so that provide the required flow velocity that is contained in solid particle in the dilution slurry.The calculated value of the mass flow rate of the solid particle that contains in the slurry is diluted in response, and continuous catalyst is flowed remains on required value.The mass flow rate of the catalyst granules that is calculated is measured based on the density of the dilute catalyst slurry flow that flows to reactor and " online " of flow velocity, and based on the solid catalyst particle that constitutes slurry and the predetermined density of liquid diluent.
Yet, although the method improvement of above-mentioned preparation dilute catalyst the control that catalyst is flowed, the defective that they have is: rate of catalyst flow can not reliably be adjusted as the function of reaction condition in the polymer reactor.
Another problem relevant with the existing system that is used to prepare dilute catalyst be, these system relative volumes are huge and heavy, and comprise a plurality of tank bodies that are used to store the catalyst slurry of dilution sometimes.In addition, use tun and a large amount of diluents to prepare the dilute catalyst slurry and also hint out some significant defectives.Use a large amount of dilute catalysts to mean and use a large amount of diluents (as iso-butane).Yet iso-butane belongs to explosive chemicals, thereby may cause safety problem.
And when changing catalyst type in polymerization technique, a large amount of catalyst materials do not use yet, just may need processedly to fall, and this not only wastes but also involves severe environmental legislation very much.In addition, after disposing catalyst, clean bulky Preparation of Catalyst system and spend huge.
Therefore, there are following needs in the art: provide a kind of improving one's methods that be used to control to polymer reactor charging catalyst.More specifically, there is great demand in the art: the system that the catalyst slurry of dilution is delivered to continuously and reliably annular-pipe reactor.
And, usually metallocene and Ziegler-Natta catalyst (Ziegler-Natta catalysts) co-catalyst with olefin polymerization being used, this can significantly increase to polymerization efficiency and be higher than 1,000,000 polymer unit/catalyst units.Disclose and many co-catalyst has been introduced method in the polymer reactor.For example certain methods comprises co-catalyst is directly introduced in the polymer reactor.Yet these methods do not allow to make before entering reactor co-catalyst to contact with catalyst, although for effective catalyst-catalyst mixture will be provided, need so pre-contact especially.Another method is included in before catalyst and the co-catalyst introducing polymerisation medium, makes their contacts.Yet, in the later case, notice such fact: begin employed catalyst system in polymerisation and have maximum activity, this may be difficult to be avoided runaway reaction and be easy to relate to the caking that forms focus (hot spots) and emerge molten polymer.
Given this, the conclusion that draws is to need below also existing in this area: be provided at and control catalyst improving one's methods to the polymer reactor charging during co-catalyst contacts in advance.
Therefore, overall purpose of the present invention is to provide improved method and apparatus in order to optimize the introducing of catalyst to polymer reactor.Specific purposes of the present invention are that the supply of catalyst in the poly polymer reactor of preparation that commercialization is provided in oil suspension or the hydrocarbon solution optimized.More specifically, the present invention also aims to provide a kind of apparatus and method from catalyst stream to the speed of the poly polymer reactor of preparation that can effectively control.
Purpose of the present invention provides and a kind ofly is used for controlling the catalyst charge that contacts in advance with co-catalyst to the apparatus and method that prepare poly polymer reactor.
The present invention also aims to provide and is used for improve the method and apparatus of control at the reactor ethylene polymerization.
Summary of the invention
The invention provides a kind of apparatus and method, it is used for preparing catalyst slurry and catalyst slurry is supplied to polymer reactor, and is used for control with the poly polymer reactor of catalyst slurry injection preparation.Described catalyst slurry comprises the solid catalyst in the hydrocarbon diluent.
First aspect the present invention relates to be used to prepare catalyst slurry and catalyst slurry is supplied to the device for preparing poly polymer reactor in it, and it comprises:
-one or more storage container, it is used to hold concentrated catalyst slurry, and described catalyst slurry is made of the solid catalyst particle that is suspended in hydrocarbon diluent or the mineral oil,
-mixer, it is used for holding the catalyst slurry of the dilution with suitable concn that polymerisation uses, this container is connected with storage container by the one or more of pipelines that are used for described catalyst slurry is delivered to from described storage container described mixer, and described mixer have one or more of be used for will dilution catalyst slurry be delivered to the pipeline of described reactor from described mixer, and
-one or more of pipelines, the catalyst slurry that described mixer is connected with polymer reactor diluting is delivered to described reactor from described mixer, each bar pipeline is provided with membrane pump and is used for described slurry pump is delivered to described reactor thus, and described pump can be controlled according to reactant concentration in the described reactor.
The invention provides a kind of device, it can the initial catalyst slurry with concentration of using in the suitable polymerisation of preparing of catalyst, and the common commercialization of described catalyst ground provides with mineral oil, heptane or hexane form of suspension.Sometimes it is with the dried forms supply.
According to the present invention, directly catalyst is not introduced reactor by storage container (yet referring to catalyst transport vessel herein).This device also comprises mixer, and it is as " buffer " between storage container and the reactor.Term used herein " mixer " and " buffer container " are made synonym and are used.Mixer moves being lower than under the pressure of reactor pressure, has therefore eliminated under high pressure the catalyst risk of high speed injecting reactor out of control.And such mixer can slow down the discontinuous catalyst charge fluctuation to reactor.Provide another benefit of mixer to be, catalyst slurry can further be diluted to and be suitable for the concentration that polymer reactor uses, and can prepare and have slurry that suit the requirements, substantially invariable concentration.And, catalyst suitable, relative low concentration makes it possible to use membrane pump (membrance pump) with in the catalyst slurry injecting reactor, described catalyst concn is preferably 0.1-10 weight %, more preferably 0.1-4 weight %, preferred especially 0.1-1 weight %, and 0.5 weight % most preferably.Use the advantage of the catalyst slurry that diluted to be the amount of the catalyst that easier control is injected and flow.
In device of the present invention, use membrane pump to allow catalyst slurry to be delivered to described reactor with controllable rate of catalyst flow.In addition, because membrane pump can control according to reactant concentration in the described reactor, these pumps are particularly suitable for regulating rate of catalyst flow to suitable numerical value, and the polymerisation that takes place in this numerical value and the reactor is consistent.
In another embodiment, the present invention relates to a kind of device, wherein one or more of being used for comprises diluent injection device (diluent injection means) with described catalyst slurry from the pipeline that described storage container is delivered to described mixer.These diluent injection devices be particularly suitable for making catalyst slurry before injecting reactor by on-line dilution, and be particularly suitable for the dilute catalyst slurry and will be delivered to mixer from storage container at slurry simultaneously.
In another preferred embodiment, the present invention relates to a kind of device, it also comprises the flow-speed measurement equipment (flow measuring means) that is used to measure rate of catalyst flow, and described flow-speed measurement equipment is arranged on the described pipeline that is used for the catalyst slurry of dilution is delivered to from described mixer described reactor.
With catalyst supply to another relevant issues in the field of reactor be during polymerisation, to supply co-catalyst.Disclose many methods that are used to introduce co-catalyst, for example directly co-catalyst has been introduced polymer reactor.Yet these methods do not allow to make before entering reactor co-catalyst to contact with catalyst, although in order to form effective catalyst-catalyst mixture, so pre-contact is special needs.Another method is included in before catalyst and the co-catalyst introducing polymerisation medium, makes their contacts.Yet, under latter event, the pre-time of contact of restive catalyst and co-catalyst.
In another embodiment, therefore device of the present invention also is provided with co-catalyst distribution system (being also referred to as the co-catalyst feed system herein), be used for before described catalyst slurry is supplied to described reactor, making the co-catalyst of appropriate amount contact reasonable time with catalyst slurry.In preferred embodiment, described system comprises co-catalyst storage container and the connected pipeline that is used to shift described co-catalyst.In another preferred embodiment, described pipeline is provided with contacting container (contact vessel), and it is used to prolong described co-catalyst and described catalyst slurry in described ducted time of contact.
On the other hand, the present invention relates to catalyst slurry is supplied to the optimization method in the poly polymer reactor of preparation in it, it comprises following steps:
-concentrated catalyst slurry is provided in one or more storage container, described concentrated catalyst slurry comprises the solid catalyst particle that is suspended in hydrocarbon diluent or the mineral oil,
The described concentrated catalyst slurry of-dilution, to obtain to be used for the suitable concn of polymerisation, the dilute catalyst slurry is delivered to it in mixer by described storage container simultaneously thus, keeps the catalyst slurry of described dilution in described mixer,
Catalyst slurry in the described storage container of-optional further dilution, and
-by means of being arranged on each ducted pumping equipment (pumping means),, described catalyst slurry is pumped to described polymer reactor from described mixer with controlled flow velocity via one or more of pipelines.
Method of the present invention has been improved the injection of catalyst in the polymer reactor with suitable, controlled and limited flow velocity, and described catalyst is with the commercialization form supply of solid particle.Therefore, this method relates generally to the catalyst slurry that will concentrate and is delivered to buffer container, and before catalyst was injected into reactor, it diluted in buffer container and keeps suitable concn.This method does not relate to catalyst from the direct injecting reactor of storage container.Especially, feature of the present invention also be catalyst slurry before being injected into reactor in pipeline (in line) diluted, and especially diluted when described storage container is delivered to mixer, wherein said catalyst slurry is optional further to be diluted.
The present invention provides a kind of method especially, and it can supply catalyst slurry to reactor with complete controlled catalyst charge flow velocity.Method of the present invention comprises: by measuring concentration of reactants in described reactor, be controlled to be suitable speed with the speed that described catalyst slurry is flowed to described reactor.Method of the present invention can accurately be regulated (fine tune) catalyst charge to reactor advantageously according to the function of polymerisation in the reactor.Can control polymerization speed of production in the reactor to the catalyst charge of reactor by control.According to this point, coming with suitable charging rate is that reactor provides sufficient and optimizes the catalyst slurry of concentration, and the result has significantly improved the productive rate in the polymer reactor and the denseness (consistency) of polymerizate.Substantially the polymerizate performance of polymerisation generation and the fluctuation of quality aspect have been avoided.In fact, by the pipeline that buffer container is connected to reactor is equipped with pump (being preferably membrane pump), can accurately regulate to reactor supply catalyst according to polymerisation, described pump can and be regulated according to reactant concentration control in the reactor.
More specifically, be equipped with pumping equipment on each bar pipeline, preferred diaphragm pump is used for catalyst slurry is delivered to polymer reactor from mixer.These pumps are guaranteed with controllable flow velocity catalyst slurry to be delivered to described reactor.And, owing to can control and regulate membrane pump,, flow with the catalyst that is adjusted to described reactor according to the polymerisation in the described reactor so can control these pumps according to the function of reactant concentration in the reactor.
According to the present invention, apparatus and method of the present invention can be with suitable rate of catalyst flow, the catalyst slurry of optium concentration is supplied to reactor, thereby can improves the productive rate of polymerisation in the reactor significantly.
Therefore the present invention provides a kind of apparatus and method, described apparatus and method are by optimizing catalyst to the supply process of described reactor and the device that this process of enforcement is provided, thereby to being optimized of polymerisation in the reactor, this apparatus and method design is simple, rugged construction and cost saving.The quality that term " optimization polymerisation " refers to improve polymerisation efficient and/or improves prepared polymerizate.
Method and apparatus of the present invention is particularly useful for the polymerization process of ethene, and is preferred for preparing bimodal polyethylene (bimodal polyethylene).
The all various feature imbodies of the present invention in the appended claims and constitute a disclosed part.For understanding the present invention, its operational advantage better and by using the specific purposes that it is realized, with reference to the accompanying drawing and the descriptive content that show the preferred embodiment for the present invention.
Description of drawings
Fig. 1 describes the schematic diagram of the preferred implementation of apparatus of the present invention in detail, and described device is used for controlling the catalyst injection of polymer reactor.
Fig. 2 has at length represented the preferred implementation of the metering valve that uses in apparatus of the present invention, and the catalyst slurry that described metering valve is used to control from storage container to mixer is carried.
Fig. 3 is the schematic diagram of another preferred implementation of apparatus of the present invention, and described device is used to prepare catalyst and catalyst is supplied to polymer reactor.
Fig. 4 is the schematic diagram of monocycle pipe polymer reactor (single loop polymerization reactor).
Fig. 5 is the schematic diagram of expression double loop polymerization reactor (double loop polymerization reactor).
The specific embodiment
The present invention especially is fit to supply process to polymer reactor with catalyst.Below with reference to slurry loop polymer reactor, specifically describe the present invention with catalyst supply polymerising ethylene in it.For example, the polymerization process of ethene can be carried out in annular-pipe reactor." vinyl polymerization " that be fit to includes but not limited to ethylene homo, ethene and more senior 1-olefin comonomer such as butylene, 1-amylene, 1-hexene, 1-octene or the copolymerization of 1-decene.Vinyl polymerization comprises: reactant is supplied to reactor, and described reactant comprises monomer ethylene, light hydrocarbon diluent, catalyst and optional comonomers and hydrogen.In embodiments of the present invention, described comonomer is a hexene, and described diluent is an iso-butane.
In particularly preferred embodiments, the present invention relates to the method in the polymer reactor of catalyst supply preparation bimodal polyethylene in it." bimodal pattern PE " is meant the PE of two reactor made using the polyphone connection.Yet, should understand and be used to improve and optimize the reactor that method that catalyst supplies with to polymer reactor equally also can be fit to take place in it other types of polymerization reaction among the present invention.
According to the present invention, the term among the present invention " catalyst " be defined as the rate variation that makes polymerisation and in reaction nonexpendable material itself.Can use and anyly can make ethylene polymerization catalysts.The example of this catalyst can be mentioned Ziegler-natta catalyst, based on the catalyst and the metallocene catalyst of vanadium or chromium.According to one preferred embodiment, described catalyst is metallocene catalyst or chrome catalysts.According to another preferred embodiment, described catalyst can also be a Ziegler-Natta catalyst.In another particularly preferred embodiment, described catalyst can comprise any catalyst that is supported on the silicon carrier.
Can prepare catalyst slurry by different way.A kind of mode comprises from solid catalyst particle and prepares catalyst slurry that described solid catalyst particle is suspended in the suitable dilution agent, in hydrocarbon.Usually, this catalyst slurry can be delivered directly in the polymerization container, to contact with monomer reactant.
Catalyst slurry can also be commercially available with the form that is suspended in the solid catalyst particle in the mineral oil.By being provided with the conduit of appropriate pump, the industrial container that will contain catalyst in oil suspension is connected with described reactor, can realize the direct injection with this catalyst slurry.This pump generally is to be suitable for the liquid that pumping has a large amount of solids (for example, the solid particle in the crude oil).
The example of this class pump has known Moineau pump and progressive cavity pump usually, and can be commercially available.
Disclose in the prior art and severally supplied method to polymer reactor with catalyst.For example, US 3,846, and 394 disclose the method for introducing the Ziegler-Natta catalyst slurry in reactor.This method comprises preparation Ziegler-Natta catalyst slurry, carries slurry from storage area to metering region via feed pipe, and slurry is introduced in the reactor.Material is back in the Ziegler-Natta catalyst pipeline in monomer and other reactor, this method uses the diluent that Ziegler-Natta catalyst is inertia to provide to catalyst charge pipeline to be washed, and described diluent is introduced the pipe downstream of described metering region.
Be called the olefinic polymerization of Z-N system or the catalyst system that copolymerization is used, comprise by the transistion metal compound that belongs to the IV-VII of family in the periodic table of elements as catalyst on the one hand, on the other hand, comprise that organo-metallic compound by the metal of the I-III of family in this table is as co-catalyst.The most frequently used catalyst is the halo derivatives of titanium and vanadium, preferably relevant with magnesium compound.In addition, the most frequently used co-catalyst is organo-aluminium or organic zinc compound.All Z-N body catalysts are characterised in that they all produce straight chain polymer.
It is MX that Ziegler-Natta catalyst preferably has general formula n, wherein M is the transistion metal compound that is selected from the IV to VII of family, wherein X is a halogen, and n is the chemical valence of metal.Preferably, M is the metal of the IV of family, the V of family or the VI of family, is more preferably titanium, chromium or vanadium, most preferably is titanium.Preferably, R is chlorine or bromine, most preferably is chlorine.The illustrative examples of transistion metal compound is including but not limited to TiCl 3, TiCl 4In the particularly preferred embodiment of the present invention, described catalyst is titanium tetrachloride (TiCl 4) catalyst.
Ziegler-Natta catalyst is provided in promptly to be deposited on the solid carrier on the carrier usually.This carrier should be an inert solid, its not with conventional Ziegler-Natta catalyst in any component generation chemical reaction.This carrier is silica or magnesium compound preferably.Be used for providing the example of the magnesium compound of support source that magnesium halide, dialkoxy magnesium, alkoxyl magnesium halide, zirconyl oxyhalides magnesium (magnesiumoxyhalide), dialkyl magnesium, the carboxylate of magnesia, magnesium hydroxide and magnesium are arranged to catalytic component.
Term " metallocene catalyst " is used to describe any transient metal complex that is made of " folder " metallic atom between one or two parts.One preferred embodiment in, metallocene catalyst has formula M X, wherein M is the compound that is selected from the transition metal of the IV of family, wherein the part be made up of one or two cyclopentadienyl groups (Cp), indenyl, fluorenyl or their derivative of X.The illustrative examples of metallocene catalyst includes but not limited to Cp 2ZrCl 2, Cp 2TiCl 2Perhaps Cp 2HfCl 2
Metallocene catalyst is provided on the solid carrier usually.This carrier should be an inert solid, and it does not have chemical reactivity to any component in the conventional metallocene catalyst.This carrier is silicon compound preferably.
In the art, known that metallocene catalyst is generally used for preparation of polyolefins, especially polyethylene.Metallocene catalyst is the compound of the IV of family transition metal such as titanium in the periodic table, zirconium, hafnium etc., and has the coordination structure that is made of metallic compound and the part that is made of one or two cyclopentadienyl groups (Cp), indenyl, fluorenyl or their derivative.In olefinic polymerization, use metallocene catalyst that various advantages are arranged.Metallocene catalyst has high activity, with the polymer phase ratio that uses the Ziegler-Natta catalyst preparation, can prepare the polymer with improvement physical property.As well known in the art, metallocene catalyst uses with the co-catalyst such as the mixture of the lewis acid of organo-metallic compound or non-coordination and alkyl aluminum usually.The key of metallocene catalyst is the structure of complex.Depend on required polymer, can change the structure of metallocene and geometry (geometry) to adapt to the producer's concrete needs.Metallocene comprises independent metal site (single metal site), and this can have more controls to the branching and the molecular weight distribution of polymer.Monomer is inserted between metal and the polymer growth chain.
Chromium-type catalyst refers to by chromated oxide being deposited on the catalyst that obtains on carrier such as silica or the alumina supporter.The illustrative examples of chrome catalysts includes but not limited to CrSiO 2Perhaps CrAl 2O 3
Usually use co-catalyst to improve the activity of Ziegler-Natta catalyst or metallocene catalyst.Term " co-catalyst " is defined as and can be used for combining to improve the catalyst of other activity of such catalysts of polymerisation and availability (availabity) with another kind of catalyst herein.In preferred embodiment, described co-catalyst is to be applicable to the catalyst that combines with Ziegler-Natta catalyst or metallocene catalyst.Co-catalyst is used to improve the polymerization activity of Ziegler-Natta catalyst or metallocene catalyst.Broadly, the organo-metallic compound of the metal of the I to III of family can be used as co-catalyst of the present invention in the periodic table.Be applicable to that the catalyst that combines with metallocene catalyst comprises organo-metallic compound, the mixture of perhaps non-coordination lewis acid and alkyl aluminum.
In particularly preferred embodiments, described co-catalyst is to be suitable for the catalyst that combines with Ziegler-Natta catalyst or metallocene catalyst, and is optional by the AlR that has of halo 3Perhaps AlR 2The organo-aluminum compound of Y general formula, wherein R is the alkyl with 1-16 carbon atom, and R is identical or different, and Y is hydrogen or halogen.The example of co-catalyst is including but not limited to trimethyl aluminium, triethyl aluminum, diisobutyl aluminium hydride, triisobutyl aluminium, three hexyl aluminium, diethyl aluminum chloride, perhaps diethylaluminum ethoxide.The preferred especially triisobutyl aluminium (TIBAL) of the used co-catalyst of the present invention.
As used herein, term " catalyst slurry " refers to comprise the catalyst solid grains of composition of suspended form.Term " concentrated catalyst slurry " refers to comprise the catalyst solid grains of composition of suspended form, and wherein catalyst concn is at least greater than 10 weight %.Term " catalyst slurry of dilution " refers to comprise the catalyst solid grains of composition of suspended form, and wherein catalyst concn is less than or equal to 10 weight % at least.
The embodiment of apparatus of the present invention of following discloses meets preparation and injects the desired equipment of a kind of catalyst.If desired two kinds or more kinds of (different) catalyst are supplied to reactor, two covers or device how of the present invention then can be provided or use apparatus of the present invention to prepare catalyst mixture and supply.
In first embodiment, the present invention relates to be used for being controlled at the device of polymer reactor injecting catalyst slurry, it comprises:
-one or more storage container, it is used for the storage catalyst slurry, and described catalyst slurry is made of the solid catalyst in the hydrocarbon diluent,
-mixer, this container is connected with described storage container by means of described conveying equipment (transferring means), and described conveying equipment is used for described catalyst Yu Jiang is diluted to the suitable concn that polymerisation is used, and
-one or more of pipelines, described mixer is connected with polymer reactor with the catalyst slurry with described dilution is delivered to described reactor from described mixer, each bar pipeline is provided with pumping equipment thus, is used for described slurry pump is delivered to described reactor.
The embodiment of this device is particularly useful for control metallocene catalyst or chrome catalysts slurry is injected the poly polymer reactor of preparation in it.
In preferred embodiment, be used for the described one or more of pipelines that catalyst slurry is delivered to described mixer from described storage container are comprised and be used for described catalyst slurry is delivered to first pipeline of mixer from described first storage container, its with second pipeline that is used for described catalyst slurry is delivered to mixer from described second storage container via the pipeline that is connected described first equipment and described second equipment can be interconnected (interchangable).
Another preferred embodiment in, be used for described catalyst slurry is delivered to the described pipeline of mixer from storage container, be equipped with metering valve in the downstream of connecting line respectively.
Below with reference to for describing embodiments of the present invention to the control of the preparation metallocene catalyst of poly polymer reactor offered load on the silica that is impregnated with MAO (MAO).This preferred embodiment in, iso-butane is as the diluent of metallocene catalyst.As for the co-catalyst of metallocene catalyst, can mention the triisobutyl aluminum cocatalyst, be referred to herein as TIBAL.Yet, should understand the catalyst that this equipment is applicable to other type, chrome catalysts for example is applicable to the co-catalyst of other type too.
Refer now to Fig. 1, diagram device of the present invention.This device comprises one or more catalyst stores container, perhaps so-called slurry bucket or jar 2, and it contains the solid-liquid slurry and the isobutane diluent of metallocene catalyst.This slurry is fed to the mixer 3 from the combination and the pipeline 15 of slurry pot 2 via pipeline 6,7, in mixer 3, this slurry is diluted to suitable concentration.In addition, this device also comprises one or more of pipelines 4, pipeline 4 is connected to polymer reactor 1 with mixer 3, and via pipeline 4, by means of the pumping equipment 5 that is equipped with in these pipelines 4 catalyst slurry is pumped into the reactor 1 from described mixer 3.
Metallocene catalyst can be provided in the drum or tote box that is purchased with dried forms.Usually these drums that dry catalyst powder is housed can not under high pressure be operated.For example, the pressure in these drums is about the 1.1-1.5 crust, preferred 1.3 crust.Depend on employed diluent, may need with this more the catalyst under the high pressure condition introduce in the storage container 2.Therefore use suitable system, preferably this catalyst is delivered to from these drums (drum) and is applicable to the storage container of under high pressure more, operating 2, if diluent needs like this.For example, when using isobutene, be this situation, because this diluent only is only liquid under elevated pressures.For example, just do not need storage container 2, under lower pressure because this diluent is a liquid using under the situation of hexane as diluent.According to preferred embodiment,, preferably carry or gravity via pipeline 27 from drum 26 by means of nitrogen pressure, metallocene catalyst is provided to storage container 2.Yet, to other form of storage container supply catalyst obviously also be fit to and belong to scope of the present invention.In selectable embodiment, also can be with providing metallocene catalyst in the industrial container that is suitable under the high pressure of 7-16 crust, operating.Under these circumstances, think that industrial container is exactly a storage container 2, and directly supply catalyst to mixer 3 from this industrial container.By means of control valve, isobutane diluent is introduced storage container 2.
In storage container, metallocene catalyst is stored under the iso-butane pressure of no liquid alkene, preferred 7-16 crust.Pressure in storage container preferably is lower than pressure in the reactor, leaks to reactor from storage container to avoid catalyst.Because this container does not have mixing plant, catalyst sedimentation in storage container 2.
By means of conveying equipment this catalyst is delivered to the mixer 3 from storage container 2 subsequently, the described catalyst of dilution is to obtain to be applicable to the concentration of polymerisation in mixer 3.Preferably, will contain this catalyst mixture in the storage container 2 of higher proportion solids content, be supplied to mixer 3 by pipeline 6,7.As directed, two storage containers are connected to common mixer 3 by different pipeline 6,7.Under these circumstances, the catalyst mixture in the pipeline 6,7 is before being supplied to mixer 3, and preferred row advances in the common pipeline 15.Yet,, also can only provide storage container 2 according to the present invention.For avoiding catalyst to remain in the storage container 2,, make remaining catalyst transport to mixer 3 with this container of isobutane flush.
In particularly preferred embodiments, pipeline 6,7 interconnects by connecting line 8.This pipeline 8 makes it possible to use different storage containers 2 according to all pipelines 6,7 that are equipped with.For example, as shown in Figure 1, two storage containers 2 are being provided, have separately under the situation of pipeline 6 or 7, pipeline 6 is used for described catalyst is delivered to mixer 3 from first storage container 2, pipeline 7 is used for described catalyst is delivered to mixer 3 from second storage container 2, and pipeline 6 is interconnected via the pipeline 8 that is connected described first pipeline 6 and described second pipeline 7 with pipeline 7.This being interconnected allows when carrying catalyst to interrupt via pipeline 6, via second pipeline 7 to mixer 13 output catalysts.
Each bar pipeline 6,7 preferred metering valve 9 that are equipped with makes with controlled flow velocity to mixer 3 supply catalyst.These valves preferably are provided to the downstream of connecting line 8.Pressure differential between storage container 2 and mixer 3 provides power, so that catalyst is supplied to mixer.
Metering valve 9 with the catalyst transport of predetermined to mixer 3.The catalyst slurry of being discharged by this valve is carried into mixer by iso-butane.Therefore, preferably each bar pipeline 6,7 also is equipped with the connected interface 24 of energy, so that use diluent flush.Described interface preferably is arranged on the downstream of valve 9.
In preferred embodiment, metering valve 9 is ball check valve or batch inlet valve (shotfeeder valves).
Fig. 2 explanation is applicable to the ball check valve arrangement of apparatus of the present invention.Yet obviously the valve of other type also can be used for device of the present invention.With reference to figure 2, Fig. 2 has represented the preferred embodiment of valve, it comprises the valve body 16 with import 17 and outlet 18, parts 19, the spherical plunger 21 that contains metering cavity (metering chamber) 20, described parts 19 are rotatable so that is communicated with at least two positions with import 17 and outlet 18 in valve body 16, and described spherical plunger 21 moves back and forth in cavity when parts 20 rotations.The working mechanism of this valve comprises following order: injection, valve actuation and discharge the catalyst slurry of certain volumes from storage container 2 to mixer 3.Operating period, when valve was in primary importance, the concentrated slurry flow of fixed amount was crossed import 17 and is full of cavity 20 in the valve 9.When valve turns to the second place, discharge described amount to mixer 3.Therefore, valve 9 is carried the concentrated slurry of fixed volume from storage container 2.
The more detailed mechanism of action of this specific ball check valve 9 is as follows.Valve 9 injects or is full of the catalyst and the diluent mixture of predetermined when primary importance.Periodically, this ball check valve turns to the second place, thereby the mixture of this volume enters mixer 3 from the valve discharge.Then ball check valve 9 refill or refill predetermined mixture to prepare to go back to primary importance, just discharge at the mixture of this position second volume and to enter the mixer 3 from valve 9.Like this, the cycling by metering valve 9 realizes that the slurry that concentrates flows into mixer 3 from storage container 2.The cycle period decision catalyst of this valve flows into the speed of mixer 3.For example, if this cycle period is elongated, then rate of catalyst flow descends.
Because high dilution and use membrane pump, advantageously the allowing with this catalyst from controlled flow velocity to mixer 3 supply catalyst from the feed system of storage container 2 to mixer 3.In addition, because the catalyst flow that flows to mixer 3 that regulated by valve 9 depends on the dosage (concentration) of catalyst and diluent in the mixer 3, so this feed system allows the concentration of the catalyst slurry in mixer 3 to remain on substantially invariable level.Of the present invention preferred embodiment in, the concentration of catalyst slurry remains on substantially invariable level in the mixer.According to the present invention, fully control the ratio between diluent and the catalyst.By controlling fully, and make this become possibility by discharging an amount of iso-butane to mixer by means of this catalyst charge system and 9 pairs of catalyst charges of metering valve from storage container.
The catalyst waste material can be sent to and dump container (dump vessel) 28, and it preferably is equipped with mixing plant 25 and contains the mineral oil that is useful on neutralization and removes refuse.Dumping container preferably links to each other with the catalyst charge pipeline 6 or 7 of metering valve 9 upstreams by means of pipeline 29.Dump container 28 and also preferably be connected to mixer 3, in order to carry the catalyst waste material by means of pipeline 23.This dumps container and is provided with heating container, and as steam jacket, wherein iso-butane is evaporated and delivers to distillation or delivers to burner (flare).For fear of when carrying the iso-butane of evaporation, carrying catalyst debris, dump container 28 and be equipped with protection filter (guide filter).Dumping container 28 also is equipped with pressure control equipment (pressurecontrolling means, it is used for controlling described container pressure.From dump container 28, remove evaporation diluent residual catalyst waste material afterwards,, and enter the refuse of removing in the bucket and further destruction preferably by means of the discharging system that is arranged on container 28 bottoms (draining system).
According to the present invention, metallocene catalyst is delivered to mixer 3 from storage container 2.Valve by in pipeline 6 and the operation of 7 places provides iso-butane liquid stream to mixer 3.Another effect of this liquid stream is the dense slurry of dilution.Mixer 3 all can move being full of under the liquid (full of liquid) or not being full of under the liquid.Preferred mixer 3 moves being full of under the liquid, has the middle phase (interphase) of nitrogen because if exist, then catalyst slurry can be in container sedimentation or adhere on the wall.
Preferably, to be diluted to concentration with hydrocarbon diluent in mixer 3 be 0.1-l0 weight % to the metallocene catalyst slurry.More preferably, it is 0.1-4 weight % that this slurry is diluted to concentration with hydrocarbon diluent, more preferably 0.1-1 weight %, even more preferably 0.5 weight %.In greater detail following, the dilution slurry that preparation has these concentration can help further utilizing membrane pump 5 with in the slurry injecting reactor 1.Mixer 3 also is equipped with agitator 25, to keep the uniformity of slurry.
By one or more of pipelines the catalyst slurry of dilution is discharged and provided to polymer reactor 1 by these pipelines from mixer 3.Every pipeline 4 is equipped with pumping equipment 5, and its control is carried and injection metallocene catalyst slurry to reactor l.In particularly preferred embodiments, described pumping equipment is a membrane pump.Pipeline 4 is preferred upwards away from mixer 3, preferably is in to be higher than 10 ° angle, and more preferably is in and is higher than 30 ° angle.In addition, the pipeline that is preferably placed under the pumping equipment 5 conducts catalyst slurry downwards, preferably is in to be higher than 10 ° angle.Because with such setting, pump 5 interrupt or situation about stopping under slurry discharge (settle away) from pump 5 easily, can also avoid obstruction in the pumping equipment 5 so the effect that has improved pumping equipment 5 is set like this.Yet, can obtain pipeline 4 and wash fully if should understand, do not need pipeline to extend downwards.
As shown in Figure 1, pipeline 4 is further in import 30, outlet 33 or be provided with isobutane flush equipment (isobutene flushing means) in the both sides of membrane pump 5, and isobutane flush equipment 30,33 makes isobutane flush piping 4 and keeps pipeline 4 and pumping equipment 5 not to stop up.Preferably, by means of isobutane flush equipment 33, pipeline 4 to the reactor in membrane pump 5 downstreams is washed continuously.Can be interrupted flushing membrane pump 5 upstream line 4 by means of isobutane flush equipment 30.Be used for mixer 3 is connected to reactor 1 if be equipped with different pipeline 4, a then common pipeline operation with an active pumping equipment 5, and other pipeline 4 and pumping equipment 5 do not move, but will remain on standby mode.Under latter event, the pipeline 4 in pump 5 downstreams is preferably washed by proper diluent stream.The pipeline 4 of pump 5 upstreams can be interrupted flushing.In addition, two-way valve 31 can be installed on the pipeline 4, so that pumping equipment 5 is never shut down.
Correct control metallocene catalyst is to the flow velocity of reactor and to enter reactor with flow velocity pumping catalyst slurry controlled and restriction be important.Unexpected speed to reactor can cause runaway reaction.Flow fluctuation (fluctuating flow) to reactor can cause efficient to reduce and the product quality fluctuation.Therefore, in particularly preferred embodiments, syringe pump 5 flow velocitys are by reactor 1 action control.
Pumping equipment especially can be according to the function control of reactant concentration in the described reactor.Preferred described concentration of reactants is monomer such as the concentration of ethene in reactor.Yet, should know that membrane pump also can be controlled according to the function of the concentration of other reactant such as copolymerization-monomer or hydrogen in the reactor.By using membrane pump 5, the present invention is flowed to catalyst provides good control.Specifically, by regulating barrier film throw of pump or frequency the speed that metallocene catalyst flows to reactor is controlled.And flow rate pump is by ethylene concentration control in the reactor.If ethylene concentration height in the reactor then adds more multi-catalyst in reactor and vice versa.By this way, considered that vinyl polymerization rate variations and actual production speed and product characteristics do not have remarkable fluctuation.Consider the vinyl polymerization rate variations and under the condition of optimum catalyst charging, can realize polymerisation.
When the operation of the above-mentioned embodiment of apparatus of the present invention begins, carry out following consecutive steps.At first, mixer 3 is full of the diluent iso-butane with the pipeline that is positioned under the valve 9.Then, provide iso-butane to the storage container that is positioned at valve 9 upstreams and pipeline 6 and connecting line 8.Then, valve 9 puts into operation immediately, wherein opens valve behind flushing reactor 1, and catalyst is passed through pipeline 4 injecting reactors.
In another embodiment, the present invention relates to a kind ofly be used to prepare catalyst and with its device that is supplied to polymer reactor, it comprises:
Be applicable to (storage) container that comprises the catalyst concentration slurry, described catalyst slurry comprises the catalyst solid particle that is suspended in the mineral oil,
Be used for described catalyst slurry is diluted to the buffer container of the concentration that is suitable for the polymerisation use, described buffer container is connected the pipeline of catalyst slurry from described (storage) container transport to buffer container that concentrates by one or more of with described (storage) container, and be provided with one or more of catalyst slurries and be delivered to the pipelines of described reactor from described buffer container dilution
Be provided in and be used on every pipeline catalyst slurry from described container transport to the pump of described buffer container, and
Be provided in the pump that is used for the catalyst slurry of dilution is delivered to from described buffer container described reactor on every pipeline.
The embodiment of above-mentioned relevant apparatus of the present invention is particularly useful for dissimilar catalyst, for example chromium-type, metallocene and Ziegler-Natta catalyst, and the catalyst that provides with the solid particle that is suspended in the mineral oil is provided.
The embodiment of apparatus of the present invention can be delivered to buffer container with the catalyst slurry that concentrates from storage container before slurry is supplied to reactor.Therefore, another preferred embodiment in, device of the present invention is provided, wherein on pipeline, be equipped with pump, be delivered to buffer container in order to the catalyst slurry that will concentrate from storage container, preferably comprise progressive cavity pump.This pump is particularly suitable for a large amount of solids of pumping, as the catalyst solid particle in mineral oil.
And, the invention provides a kind of device, it can regulate catalyst flowing to described reactor according to the function of polymerisation in the described reactor.Therefore, another preferred embodiment in, be provided in be used on the pipeline with the dilution catalyst slurry comprise membrane pump from the pump that described buffer container is delivered to described reactor.The advantage of such pump is: it can control rate of catalyst flow.And such pump especially can be regulated according to the function of concentration of reactants in the described reactor.By means of feedback mechanism, the speed of catalyst stream to reactor be adjusted and be finely tuned to membrane pump can according to the function of concentration of reactants in the described reactor.
In addition, apparatus of the present invention have the advantage that can be used for the different batches catalyst.This device does not need the each hyperphoric new industrial container that comprises catalyst to be connected with system.
As mentioned above, the embodiment of apparatus of the present invention is particularly useful for dissimilar catalyst, for example chromium-type, metallocene and Ziegler-Natta catalyst.Yet, provide Ziegler-Natta catalyst below with reference to the polymer reactor that is used for to polymerising ethylene, especially the apparatus and method of titanium tetrachloride (TiCl4) catalyst explanation this embodiment of the present invention.As the co-catalyst of Ziegler-Natta catalyst, can mention the triisobutyl aluminum cocatalyst.Yet, as mentioned above, should clear and definite apparatus of the present invention be applicable to the catalyst and the co-catalyst of other type too.
Preferred implementation with reference to figure 3 explanation apparatus of the present invention.Usually, apparatus of the present invention comprise the container 2 of the catalyst that is used for receiving oil suspension, and the buffer container 3 that is used to prepare and store the dilute catalyst slurry of the suitable concn that is applicable to polymerisation.
Via pipeline 40 catalyst slurry that concentrates is delivered to buffer container 3 from container 2 by means of pump 50, continuously is delivered to reactor via the catalyst slurry that one or more of pipelines 4 will dilute from buffering container 3 by means of pump 5 simultaneously.For clarity sake, there is the CONSTRUCTED SPECIFICATION of closing valve, pump etc. to omit in the drawings, provides these contents to belong to techniques well known.
By of the present invention, the Ziegler-Natta catalyst titanium tetrachloride (TiCl that is provided 4) be the suspension of solid particle in mineral oil or hexane or heptane, be contained in the drum that is purchased.It can also provide with dried forms.By means of nitrogen pneumatic conveying or gravity, this catalyst is transported to container 2 from the drum that is purchased.By adding mineral oil, also can using other hydrocarbon instead and adjust this catalyst concn in the container 2.
Generally, pressure is about the 7-16 crust in the container 2.Slurry refers to " concentrating " or " weight " slurry in the container 2, because it contains the pellet type catalyst solid of content at high proportion.Such concentration is preferably 10-50 weight %, and more preferably 20-40 weight %.
According to preferred embodiment, the Ziegler-Natta catalyst that concentrates is transported to buffer container 3 from container 2, wherein catalyst dilution is to being suitable for the concentration that polymer reactor uses.Therefore buffer container 3 outfit devices 34 are used for to buffer container 3 supply suitable diluent.The catalyst concentration that is supplied to buffer container 3 via pipeline 4 is by the diluent dilution via pipeline 34 supplies, with the catalyst slurry that obtains at buffer container 3 to dilute.Buffer container 3 can move when being full of liquid or not being full of.Preferably, buffer container 3 moves when being full of liquid, has the middle phase of nitrogen because if exist, then catalyst slurry can be in container sedimentation or adhere on the wall.
When using TiCl 4As catalyst, can use the hydrocarbon such as hexane or iso-butane to come dilute catalyst, with the catalyst slurry that obtains to dilute.Yet, use hexane to be as the main disadvantage that diluent prepares catalyst, common a certain proportion of hexane remains in the final polymerizate, and this is undesirable.On the other hand, iso-butane is easier to handle, purifies and be used in polymerization process than hexane.For example, since in the polymerization process of ethene iso-butane in reaction as diluent, so can easily be used for polymerization process once more as the iso-butane of catalyst diluent.Therefore, in preferred embodiment iso-butane as TiCl 4The diluent of catalyst.Iso-butane exists with gaseous state under room temperature and atmospheric pressure usually.For obtaining the catalyst slurry of liquid iso-butane with the preparation dilution, buffer container 3 preferably runs on the pressure limit of 8-17 crust, and preferred pressure range 4-5 crust.Pressure preferably is lower than pressure in the reactor in the buffer container 3, leaks to reactor from the buffering container to avoid catalyst.
Before Ziegler-Natta catalyst is transported to buffer container 3 from container 2, iso-butane is imported container 3.Container 3 is provided with the input system (inlet system) 34 that is used to supply this diluent.Stir containers 2 and buffering container 3 by being arranged on stirring in the described container or mixing arrangement 25, with that keep respectively concentrating and catalyst slurry homogeneous dilution.Buffer container 3 is preferred enough greatly to hold enough catalyst slurries and enough big so that day cubical content (day vessel capacity) is suitable with the time of preparation new lot.This can guarantee continuous production and obtain catalyst in polymer reactor.What can be used as selection is to provide second container 2 with preparation new lot material.
Because the slurry in the buffer container 3 contains the pellet type catalyst solid of low ratio content, so this slurry refers to " dilution " slurry.The slurry concentration of this dilution is 0.1-10 weight %, and preferred 0.1-5 weight %, and more preferably 0.5-4 weight %.The benefit that preparation has the catalyst slurry of these concentration is further to use membrane pump (diaphragm pump) to be used for injecting the catalyst slurry of dilution at reactor 1, as following institute in greater detail.If use the catalyst slurry of other concentration, obviously can use the pump of other type.
Preferably finish from container 2 and carry Ziegler-Natta catalyst to buffer container 3 by one or more of pipelines 40.For Ziegler-Natta catalyst is delivered to buffer container 3 from container 2, on each bar pipeline 40, be equipped with pump 50.In preferred embodiment, described pump 50 comprises following pump, and it is suitable for the liquid that pumping contains a large amount of solids, as the solid particle in the crude oil, otherwise can damage the more reciprocating type oil well pumped systems of general type easily.The example of this class pump has common Moineau pump or progressive cavity pump and can be commercially available.Such progressive cavity pump is with the work of Moineau principle, and it cooperates based on how much between rotating element (rotor) and the stationary element (stator).Interference engagement between rotor and the stator has produced a series of annular seal spaces, is called cavity.In stator, do centrifugal rotation by rotor and produce pump action.Liquid enters is going into the cavity of interruption-forming, and advances up to outlet forward in this cavity.Produce positive displacement, non-TRANSFER BY PULSATING FLOW, it directly is directly proportional with pump speed.This allows the flow velocity that progressive cavity pump can wide region to transmit material, from the small batch to the continuous flow.
As shown in Figure 3, pipeline 40 is preferred upwards away from container 2, preferably is in to be higher than 10 ° angle, and more preferably is in and is higher than 30 ° angle.In addition, the pipeline 40 that is arranged under the pumping equipment 50 preferably guides catalyst slurries downwards, preferably is in to be higher than 10 ° angle.Because with such setting, pump 50 interrupt or situation about stopping under slurry discharge from pump 50 easily, so the effect that has improved pumping equipment 50 is set like this, can also avoid the obstruction in the pump 50.
Illustrated in Fig. 3, pipeline 40 also preferably is equipped with damping of pulsation device (pulsation dampener), safety valve and isobutane flush equipment 300,333, perhaps is positioned at import, exports or is positioned at the both sides of slurry pump 50.Isobutane flush equipment 300,333 makes isobutane diluent can wash through piping 40, and keeps pipeline 40 and pump 50 not to stop up.Can be equipped with flow measurement equipment being used to spray on the pipeline 300,330 of iso-butane.If different pipeline 4 is provided for connection container 2 is connected to buffer container 3, a then common pipeline operation with an active pump 50, and other pipeline 40 and pumping equipment 50 do not move, but remain on standby mode.
Preferably under the proportion control of iso-butane and catalyst, the slurry that concentrates is injected buffer container, in buffer container, to have constant slurry concentration.In addition, pipeline 40 also can be equipped with the flow velocity that flow measurement equipment is convenient to measure easily the catalyst concentration slurry in pipeline 40.By the speed of control pump 50 and by measuring the density of isobutane diluent, the ratio of controlling and regulating catalyst and diluent fully.
The catalyst waste material can be sent to one or more by the pipeline 37 that is equipped with valve 39 and dump container 38, and it preferably is equipped with mixing plant and contains the mineral oil that is useful on the neutralization and removes this refuse.Preferably dump container 38 greater than buffer container 3.If prepared inappropriate catalyst, then they can be emptied to the above-mentioned container 38 that dumps from container 3.This dumps the heating container that container preferably preferably has steam jacket, and wherein diluent such as iso-butane are evaporated.For discharging iso-butane, steam jacket is preferred.The diluent that evaporates is delivered to distillation or delivered to burner.For fear of when carrying the iso-butane of evaporation, carrying catalyst debris, dump container 38 and be equipped with the protection filter.Dump container 38 and also be equipped with pressure control equipment in order to control pressure in the described container.Residual catalyst waste material after dumping container 38 removal evaporation diluents preferably by means of the discharging system that is arranged on container 38 bottoms, and enters the refuse of removing in the bucket and further destruction.
The Ziegler-Natta catalyst slurry of dilution is delivered to reactor 1 from buffering container 3 via one or more of pipelines subsequently.Preferred 0.3-2 centimetre of pipeline 4 internal diameter, and preferred 0.6-1 centimetre.Each bar pipeline 4 is equipped with pump 5, and reactor 1 is carried and be injected into to the Ziegler-Natta catalyst slurry of described pump control dilution.In particularly preferred embodiments, described pump is a membrane pump.
As shown in Figure 3, pipeline 4 is preferred upwards away from container 2, preferably is in to be higher than 10 ° angle, and more preferably is in and is higher than 30 ° angle.Because with such setting, pump 5 interrupt or situation about stopping under slurry discharge from pump 5 easily, so the effect that has improved pumping equipment 5 is set like this, can also avoid the obstruction in the pump 5.
Pipeline 4 preferably also is equipped with damping of pulsation device, safety valve and isobutane flush equipment 30,33, perhaps is positioned at import, exports or is positioned at the both sides of membrane pump 5.Isobutane flush equipment 30,33 makes isobutane diluent can wash piping 4, and keeps pipeline 4 and pump 5 not to stop up.Preferably, by means of isobutane flush equipment 33, pipeline 4 to the reactor in membrane pump 5 downstreams is washed continuously.Can be interrupted flushing membrane pump 5 upstream line 4 by means of isobutane flush equipment 30.Be used for mixer 3 is connected to reactor 1 if be equipped with different pipeline 4, a then common pipeline operation with an active pumping equipment 5, and other pipeline 4 and pumping equipment 5 do not move, but will remain on standby mode.Under latter event, the pipeline 4 in pump 5 downstreams is preferably washed by proper diluent stream.The pipeline 4 of pump 5 upstreams can be interrupted flushing.
For reducing the risk of leaking, the pressure of about 43 crust is low usually in the pressure ratio reactor for catalyst stores, for example is stored in the buffer container 3 of about 6-16 bar pressure.The preferred 45-65 crust of pressure in pump 5 downstream line 4.In order to bring the catalyst of dilution into reactor, require to have the high high pressure of pressure in container 2 and the buffering container 3 with enough pressure.
Correct control catalyst stream is to reactor and with flowing of controlled and restriction the catalyst slurry pumping to be entered reactor be important.Can cause runaway reaction to can not expecting of reactor is mobile.Fluctuating flow meeting to reactor causes decrease in efficiency and unstable product quality.Therefore, in particularly preferred embodiments, syringe pump 5 flow velocitys are controlled by the action of reactor 1.Especially, described pump can be controlled according to concentration of reactants function in the described reactor.Preferred described reactant concentration is the monomer in the reactor such as the concentration of ethene.Yet, should can also be controlled according to the function of other concentration of reactants by clear and definite membrane pump, as the concentration of comonomer in the reactor or hydrogen.By using membrane pump 5, the present invention is flowed to the catalyst that diluted provides good control.Specifically, by regulating membrane type throw of pump or frequency the speed that metallocene catalyst flows to reactor is controlled.If ethylene concentration height in the reactor then adds more multi-catalyst in reactor and vice versa.By this way, considered that vinyl polymerization rate variations and actual production speed and product characteristics do not have remarkable fluctuation.
In another embodiment, device of the present invention also is provided with the co-catalyst distribution system, is used for making the co-catalyst of appropriate amount contact reasonable time with catalyst slurry before described catalyst slurry is delivered to described reactor.If the use metallocene catalyst, preferred triisobutyl aluminium (TIBAL) is as co-catalyst.If the use Ziegler-Natta catalyst, preferred triisobutyl aluminium (TIBAL) is as co-catalyst.
With reference to figure 1 and Fig. 3, this co-catalyst distribution system 11 can comprise two co-catalyst storage containers, prepares within it and stores co-catalyst.Container be used for providing the pipeline 4 of co-catalyst to be connected to it.
The co-catalyst waste material can be sent to and dump container, and it preferably is equipped with mixing plant and contains the mineral oil that is useful on neutralization and removes this refuse.This dumps container and has heating container, and as steam jacket, wherein iso-butane is evaporated and delivers to distillation or delivers to burner.
Co-catalyst is provided in the industrial drum usually.In the storage container of co-catalyst distribution system 11, triisobutyl aluminium (TIBAL) co-catalyst provides with hexane or n-heptane solution form usually, but also can provide with pure form.Triisobutyl aluminium (TIBAL) co-catalyst is delivered into pipeline 4 from storage container via co-catalyst flow in pipes 12, and pipeline 4 links to each other mixer 3 with reactor 1.Pipeline 12 intersects at membrane pump 5 downstreams with pipeline 4 and in reactor 1 upstream.If further be equipped with flow measurement equipment 10 at pipeline 4, then co-catalyst feed pipe 12 preferred with intersect at described flow measurement equipment 10 downstreams with pipeline 4 and in reactor 1 upstream.
Ratio between time of contact between Z-N/metallocene catalyst and triisobutyl aluminium (TIBAL) co-catalyst and Z-N/metallocene catalyst and triisobutyl aluminium (TIBAL) co-catalyst has material impact for the grain size analysis and the activity of final polymerization product.Use triisobutyl aluminium (TIBAL) co-catalyst, obtain bigger polyethylene particle by activity.In addition, the pre-poly volume density and the settling efficiency (settling efficiency) that has improved reactor made that contact of triisobutyl aluminium (TIBAL) co-catalyst and catalyst.According to the present invention, the triisobutyl aluminium of appropriate amount (TIBAL) co-catalyst injected the pipeline 4 in membrane pump 5 downstreams before entering reactor 1.
If triisobutyl aluminium (TIBAL) co-catalyst flow in pipes 4, then the distance of decanting point and reactor should allow co-catalyst with catalyst to be arranged certain pre-time of contact before being fed to reactor.In order to make between metallocene catalyst and triisobutyl aluminium (TIBAL) co-catalyst there are enough pre-times of contact, be preferably 5 seconds to 1 minute, each bar pipeline 4 preferably is equipped with contacting container 13 in downstreams of co-catalyst distribution system decanting point, is used for prolonging described co-catalyst and catalyst slurry time of contact at pipeline 4.Can stir or not stir these contacting containers 13.Another preferred embodiment in, pipeline 4 internal diameters (inner diameter) are 0.3-2 centimetre, and are preferably 0.6-1 centimetre, and the diameter of contacting container 13 is preferably 1-15 centimetre, even preferred 6-9 centimetre.
In addition, in the various embodiments of apparatus of the present invention, the pipeline 4 that is provided further also is equipped with measurement device 10, so that easily measure the rate of catalyst flow in pipeline 4.These flow-speed measurement equipment 10 are Coriolis flow-speed measurement equipment preferably.Equipment 10 can be arranged between mixer 3 and the membrane pump 5 or the downstream of described pumping equipment 5.Preferably, described equipment 10 is arranged on the upstream of co-catalyst flow in pipes 11.Preferably under the proportion control of isobutane diluent and catalyst, inject slurry.By the speed of control pump 5 and by measuring the density of isobutane diluent, the ratio of controlling and regulating catalyst and diluent fully.Coriolis measuring appliance 10 energy measurements are in the flow velocity and the density of mixer 3 exit catalyst slurries, and the solid concentration of indirect determination suspension.For the solid concentration that density and density of solid particles evaluation based on slurry density, carrier fluid suspend, there is correlation.
In another embodiment, measurement device 10, and preferred Coriolis flow-speed measurement equipment can also be arranged in the pipeline 40 between storage container 2 and the mixer 3 is for example in the upstream or the downstream of these pipeline 40 septation pumps 50.
In another embodiment, catalyst slurry is with in the controlled flow velocity injecting reactor.Be used for catalyst slurry is conveyed into pipeline 4 one or more valves of outfit of reactor, preferred piston valve 22.The aperture that piston valve 22 energy closed conduits 4 are connected with reactor 1.If use different pipeline 4 to carry catalyst slurry, then only start catalyst slurry is pumped to reactor, and pump does not start in other pipeline 4, and pipeline is preferably washed by iso-butane at pump described in the pipeline 4 to reactor.
For concisely clear, in this specification and accompanying drawing, do not comprise conventional auxiliary equipment such as pump, other valve and other process equipment, because they are inoperative for the explanation of invention.Other the typical case uses in polymerization process measurement and control device are not described yet.
Obviously the number of different parts of finding out device of the present invention from this specification is relevant with the size of polymer reactor with size, and can change according to the function of reactor size.
In another embodiment, by operation according to the present invention, all pipelines, container, pump, valve etc. by flushing or with nitrogen or as the cleaning of the diluent of iso-butane can keep not stopping up.Should be appreciated that to obtain necessary flushing or cleaning device and pipeline on apparatus of the present invention, thereby avoided obstruction.
Obviously the number of different parts of finding out device of the present invention from this specification is relevant with the size of polymer reactor with size, and can change according to the function of reactor size.
Should be understood that from the present invention all indicated pressure values are preferred pressure values, it departs within about ± 1 crust of indicated pressure value usually.Obviously, all indicate force value to be lower than force value in the polymer reactor in container, pipeline etc. in this specification.
In another embodiment, should be understood that among the present invention that applied whole pipelines or pipeline all are equipped with flow measurement equipment in necessary part.
Can use apparatus of the present invention, be single polymer reactor charging.In preferred embodiment, apparatus of the present invention are used to the polymer reactor charging of being made up of two liquid phase full loop reactors (full loop reactor), comprise first and second reactors that one or more sedimentation arm (settling leg) by first reactor is connected in series, described sedimentation arm is used for slurry is expelled to described second reactor from first reactor.The reactor that is connected in series like this is particularly suitable for preparing bimodal polyethylene.Apparatus of the present invention can be applied to two reactors.The number of pipeline 4 can distribute between first and second reactors.Can also use two covers or overlap device of the present invention more, for example when using two kinds or more of catalyst.In preferred embodiment, device of the present invention can be used in single loop reactors shown in Figure 4 or the described double loop reactor of Fig. 5.
Single loop reactors 100 shown in Figure 4 is made up of many interconnected pipelines 104.Vertical section of pipeline section 104 preferably is provided with thermal jacket 105.By recirculated cooling water in these chucks of reactor, can extract heat of polymerization.Reactant is introduced in the reactor 100 by pipeline 107.By means of conduit 106, with catalyst together with optional co-catalyst or activator injecting reactor 100.Indicated as arrow 108, by one or many pumps such as axial-flow pump 101, directionally circulation in whole annular-pipe reactor 100 of polymerisation slurry.This pump can drive by motor 102.Term used herein " pump " comprises that any compression advances, increases the device of fluid pressure, for example piston or pivoting leaf wheels 103.Reactor 100 also is provided with one or more sedimentation arm 109 connecting pipes 104 and reactor 100.Sedimentation arm 109 preferably is provided with stop valve (isolation valve) 110.These valves 110 are opened under normal condition, and 109 isolation of sedimentation arm can not closed when not moving.And sedimentation arm 109 also is provided with product taking-up or vent valves 111.This vent valves is discharged polymer slurries when its standard-sized sheet.By means of one or more of product recovery line 113, shift the polymer slurries that is deposited in the sedimentation arm 109, for example arrive the product recovery area.
Fig. 5 represents double loop reactor 100/116, two single loop reactors 100 comprising that polyphone connects and 116.Two reactors 100 and 116 all are made up of many pipelines that are interconnected 104.Vertical 111 can be the valve of any kind, and it can allow the continuous part of pipeline section 104 or cyclic part (periodical section) preferably to be provided with heating jacket 105.Reactant is introduced reactor 100 by pipeline 107.By means of conduit 106, with catalyst together with in the optional co-catalyst or activator injecting reactor 100 or 116.Indicated as arrow 108, by one or many pumps such as axial-flow pump 101, directionally circulation in whole annular-pipe reactor 100,116 of polymerisation slurry.This pump can drive by motor 102.This pump can have one group of rotary blade 103.Reactor 100,116 also is provided with one or more sedimentation arm 109 that links to each other with the pipeline 104 of reactor 100,116.Sedimentation arm 109 preferably has stop valve 110.And sedimentation arm 109 also is equipped with product taking-up or vent valves 111.Downstream at the valve 111 of the outlet of reactor 100 sedimentation arms 109 is provided with triple valve 114, and it makes the polymer slurries of sedimentation in the sedimentation arm 109 can be transported to other reactor 116 by means of feed-line 112.Feed-line 112 connects the import of triple valve 114 with another reactor 116 in the exit that is arranged on reactor 100 sedimentation arms 109, at the inlet of reactor 116 piston valve 115 is set preferably.By means of one or more of product recovery line 113, shift the polymer slurries of sedimentation in sedimentation arm 109, for example arrive place, product recovery area.
The invention still further relates to catalyst slurry is supplied to optimization method to polymer reactor, in described polymer reactor, prepare polyethylene, preferred bimodal polyethylene.
In one embodiment, the present invention relates to be used for controlling the method for preparing poly polymer reactor 1 injecting catalyst slurry within it, described catalyst is made up of solid catalyst, preferably as defined above at hydrocarbon diluent, and the metallocene catalyst in the preferred iso-butane.Yet obvious method of the present invention also is applicable to be controlled at injects the chrome catalysts slurry in the polymer reactor 1.This method comprises continuous step: a) provide solid catalyst and hydrocarbon diluent in one or more storage container 2, so that in described storage container 2, obtain catalyst slurry, b) described catalyst slurry is delivered to mixer 3 by described storage container 2, the described catalyst slurry of dilution is to obtain to be applicable to the concentration of polymerisation in described mixer 3, and c) via one or more of pipe 4, by means of the pumping equipment 5 that in each bar pipeline 4, is provided with, with controllable flow velocity, the catalyst slurry of described dilution is pumped to described polymer reactor 1 from described mixer 3.Such method is particularly suitable for making to polymer reactor 1 provides metallocene or chrome catalysts to obtain to optimize.
According to preferred implementation shown in Figure 1, this method comprises: the ratio by diluent and catalyst in the control mixer 3 is transported to described catalyst slurry the mixer 3 from storage container 2 with controlled flow velocity.(described catalyst charge system is used for described catalyst slurry is fed to mixer 3 from storage container 2 by the catalyst charge system is provided, it comprises pipeline 6,7 and the metering valve 9 on the described pipeline 6,7 (preferred ball check valve or batch inlet valve (shot feeder valves)) that connects described container 2, makes it possible to control flow velocity (flow rate).The catalyst stream that flows to mixer 3 from storage container 2 is regulated and by dosage (concentration) decision of catalyst and diluent the mixer 3 by valve 9.Ratio between diluent and the catalyst is fully controlled.By by means of catalyst charge system and metering valve 9, make it possible to fully to control catalyst from the supply of storage container 2, can discharge the isobutane diluent of the appropriate amount the mixers 3 via pipeline 24.Equally, use the determined catalyst concn of measuring by Coriolis measuring appliance 10 of density, can control the amount of isobutane diluent.
In another embodiment as shown in Figure 3, the present invention relates to catalyst is supplied to the optimization method of polymer reactor 1, it comprises: a) catalyst slurry that concentrates is delivered to buffer container 3 from storage container 2, described concentrated catalyst slurry comprises the solid catalyst particle that is suspended in the mineral oil, b) by the suitable dilution agent is supplied in described buffer container 3, dilute the catalyst slurry in the described buffer container 3, obtain to have the catalyst slurry of dilution of the concentration of the polymerisation of being applicable to thus, and c) with suitable flow velocity the catalyst slurry of described dilution is transported to described reactor 1 from described buffer container 3.This method is particularly useful for optimizing Ziegler-Natta catalyst TiCl 4Be supplied in the polymer reactor 1, thus Ziegler-Natta catalyst TiCl 4, as the suspension of solid particle in mineral oil, supply is in industrial container 2 and be transported to container 3.Method of the present invention comprises via pipeline 40 catalyst slurry that concentrates is delivered to the step of buffer container 3 from storage container 2, and described pipeline 40 is provided with pump 50, preferably progressive cavity pump.
Another preferred embodiment in, method of the present invention comprises: use hydrocarbon diluent in mixer 3, preferred iso-butane is diluted to suitable concentration with catalyst slurry, and preferably being diluted to concentration is 0.1-10 weight %, and more preferably 0.1-5 weight %, and more preferably 0.5-4 weight %.For example in hydrocarbon diluent this slurry being diluted to concentration is 0.1-4 weight %, and more preferably 0.1-1.0 weight %, and more preferably 0.5 weight %.The benefit of catalyst slurry that preparation has these concentration is further to use membrane pump (membrane pump) 5, with in this slurry injecting reactor 1.Use the benefit of these pumps to be the accurate and abundant flow velocity of controlling in the catalyst slurry injecting reactor of energy.The determined catalyst concn of density that use is measured by Coriolis measuring appliance 10 is controlled the amount of isobutane diluent.
In another embodiment, method of the present invention also comprises: by diluent (preferred iso-butane) is injected the pipeline that connects storage container 2 and mixer 3, with described diluent catalyst slurry is diluted to suitable concentration.According to this embodiment, when storage container is transported to mixer, the catalyst slurry that concentrates is being diluted, the catalyst that wherein diluted remains unchanged and optional further dilution.
In another embodiment, method of the present invention comprises: control the catalyst slurry flow velocity by the reactant concentration that is determined in the described reactor 1.Preferred described reactant is the concentration (concentration) of monomer such as ethene in the reactor.Yet, should know in described reactor 1 comonomer measured in other reactant such as the reactor or the concentration (concentrations) of diluent, the scope that also belongs to the present invention and comprised.In fact, provide the membrane pump that to be controlled and to regulate according to the function of concentration of reactants the reactor with catalyst slurry from each bar pipeline of buffering container transport and supply polymer reactor, just can obtain this mechanism arrangement by giving.
As mentioned above, in some cases, catalyst is contacted with co-catalyst be need or be good.Therefore, the present invention also provides method, and it comprises: before providing described catalyst slurry to described reactor, and the step that co-catalyst is contacted with catalyst slurry.The invention provides better contact and under the situation that directly is fed to reactor when co-catalyst, form co-catalyst-catalyst mixture subsequently.Provide appropriate catalyst-catalyst mixture that more control is provided and more uniform polymerization activity level in reactor to reactor.Pre-between catalyst and the co-catalyst contacts also volume density and the deposition efficiency that granulometry for final polymerizate has positive impact and improved the polymerizate for preparing in polymer reactor.These methods can also more accurate control catalyst-co-catalyst the injection ratio.
In preferred embodiment, this method comprises: co-catalyst, preferred aforesaid co-catalyst are contacted with the described catalyst slurry that is present in the described dilution in the pipeline 4.As shown in figures 1 and 3, co-catalyst distribution system 12 preferably comprise at least one storage container and with pipeline 4 cross one another pipelines 11.Another preferred embodiment in, this method also comprises: strengthen the volume of described pipeline 4 by the part, extending contact time and strengthening co-catalyst described in the pipeline 4 contacts with the pre-of described catalyst.Catalyst has positive impact with the pre-granulometry that contacts for final polymerizate between the co-catalyst, and has improved the volume density and the deposition efficiency of the polymerizate for preparing in polymer reactor.In activation process, if too many co-catalyst contact catalyst particle, then not only catalytic activity reduces, but also produces actual infringement.Method of the present invention also helps can control the ratio that catalyst/co-catalyst is injected more accurately.Strengthen conduit volume by the part, obtain better pre-contact between co-catalyst and the catalyst.By on each bar pipeline 4, being equipped with contacting container 13, obtain the local increasing of volume.The diameter that described container 13 has is significantly greater than the diameter of pipeline 4.
Another preferred embodiment in, the invention provides with suitable flow velocity via pipeline 4 from buffering container 3 to the method for the catalyst slurry without interruption of reactor 1.Method provided by the invention can be interrupted catalyst to reactor catalyst without interruption and be flowed.Rely on this method, can guarantee does not have relevant fluctuation to reactor catalyst slurry without interruption, and this has improved the efficient of polymerisation in the reactor.
Another preferred embodiment in, in the method that the present invention relates to, use flow measurement equipment (for example, preferred Coriolis flow measurement equipment), measure by flow rate of liquid, accurately measure the speed of catalyst stream to reactor.
The invention still further relates to and use device of the present invention to prepare Ziegler-Natta catalyst, and the supply of this catalyst to polymer reactor is optimized, wherein in described polymer reactor, prepare polyethylene, preferably bimodal polyethylene.
The invention still further relates to and use device of the present invention to prepare metallocene catalyst, and the supply of this catalyst to polymer reactor is optimized, wherein in described polymer reactor, prepare polyethylene, preferably bimodal polyethylene.
The invention still further relates to and use device of the present invention to prepare chrome catalysts, and the supply of this catalyst to polymer reactor is optimized, wherein in described polymer reactor, prepare polyethylene, preferably bimodal polyethylene.
According to preferred embodiment at present, the present invention has been described, simultaneously, those skilled in the art can make rational variation and correction and these change in the scope that also belongs to described invention and appended claim.
Embodiment
Preparation embodiment by following plant-scale double loop reactor illustrates the present invention.For comparative example, use conventional catalyst charge system and control.Compare with the catalyst charge control of routine, utilize to the invention enables polymer reactor under higher slurry density, to move, and change littler.Littler standard deviation shows that the present invention can realize improvement and the higher product denseness of realization to polymerization process control.
Table 1
Embodiment Comparative example
Reactor slurry density Kilogram/cubic meter 547±3 531±6
The ethene flow Kilogram/hour 3461±23 3855±16
The reactor ethylene concentration Weight % 6.3±0.1 6.6±0.3
Flow of catalyst slurry Kilogram/hour 70.6±1.9 91.0±2.8
Catalyst slurry concentration Weight % 0.35±0.01 0.46±0.05

Claims (28)

1. be used for preparing catalyst slurry and catalyst slurry is supplied to the device for preparing poly polymer reactor in it, it comprises:
-one or more storage containers (2), it is used to hold concentrated catalyst slurry, and described catalyst slurry is made of the solid catalyst particle that is suspended in hydrocarbon diluent or the mineral oil,
-mixer (3), it is used for holding the catalyst slurry of the dilution with suitable concn that polymerisation uses, this container is connected with storage container (2) by the one or more of pipelines that are used for described catalyst slurry is delivered to from described storage container (2) described mixer (3), and described mixer be provided with one or more of be used for will dilution catalyst slurry be delivered to the pipeline of described reactor (1) from described mixer (3), and
-one or more of pipelines (4), the catalyst slurry that described mixer (3) is connected with polymer reactor diluting is delivered to described reactor (1) from described mixer (3), each bar pipeline is provided with the membrane pump (5) that is used for described slurry pump is delivered to described reactor (1) thus, and described membrane pump (5) can be controlled it according to the function of reactant concentration in the described reactor (1).
2. the described device of claim 1 wherein is used for catalyst slurry is comprised the diluent injection device from the one or more of pipelines that described storage container (2) is delivered to described mixer (3).
3. claim 1 or 2 described devices, wherein catalyst slurry is comprised first pipeline (6) that is used for described catalyst slurry is delivered to from first storage container (2) mixer (3) from the one or more of pipelines that described storage container (2) is delivered to described mixer (3), described first pipeline (6) is interconnected with second pipeline (7) by the pipeline (8) that connects described first equipment (6) and described second equipment (7), and described second pipeline (7) is used for described catalyst slurry is delivered to mixer (3) from second storage container (2).
4. the described device of aforementioned any one claim wherein is delivered to the pipeline (6,7) of mixer (3) with described catalyst slurry from storage container (2), all is provided with the metering valve (9) that is positioned at connecting line (8) downstream respectively.
5. claim 1 or 2 described devices, wherein said being used for comprises pump (50) with catalyst slurry separately from the one or more of pipelines that described storage container (2) is delivered to described mixer (3).
6. the described device of claim 5 wherein is arranged on the catalyst slurry that is used on each bar pipeline concentrating and comprises progressive cavity pump from the described pump (50) that described container (2) is delivered to described buffer container (3).
7. each described device among the claim 1-6 also comprises the flow measurement equipment (10) that is used to measure rate of catalyst flow, and it is arranged on the pipeline (4) that is used for the catalyst slurry of dilution is delivered to from described mixer (3) described reactor (1).
8. each described device among claim 1-2 and the 5-7, also comprise the flow-speed measurement equipment (10) that is used to measure rate of catalyst flow, it is arranged on the described pipeline that is used for catalyst slurry is delivered to from described storage container (2) described mixer (3).
9. each described device in the aforementioned claim, also comprise the co-catalyst feed system, it was used for before described catalyst slurry is injected described reactor, the co-catalyst of appropriate amount is contacted with catalyst slurry, and described system comprises co-catalyst storage container (11) and is connected the pipeline (12) that is used to carry described co-catalyst with it.
10. each described device in the aforementioned claim, wherein said pipeline (4) is provided with contacting container (13), and it is used for prolonging described co-catalyst and time of contact at the described catalyst slurry of described pipeline (4).
11. each described device among the claim 1-10, wherein said polymer reactor (1) is suitable for preparing polyethylene, the preferred for preparation bimodal polyethylene.
12. claim 1-4,7 and 9-11 in each described device, wherein said catalyst is a metallocene catalyst, preferably the metallocene catalyst of load.
13. each described device among claim 1-2 and the 5-11, wherein said catalyst is a Ziegler-Natta catalyst, and its general formula is MX n, wherein M is the transistion metal compound that is selected from the IV to VII of family, and wherein X is a halogen, and n is the chemical valence of metal.
14. each described device among the claim 1-13, wherein said co-catalyst are the organo-aluminum compounds of optional halo, its general formula is AlR 3Perhaps AlR 2Y, wherein R is the alkyl with 1-16 carbon atom, and R is identical or different, and Y is hydrogen or halogen.
15. catalyst slurry is supplied to the optimization method for preparing poly polymer reactor (1) in it, and it may further comprise the steps:
-concentrated catalyst slurry is provided in one or more storage container, described concentrated catalyst slurry is made of the solid catalyst particle that is suspended in hydrocarbon diluent or the mineral oil,
The described concentrated catalyst slurry of-dilution, with the suitable concn that obtains to use in the polymerisation, the dilute catalyst slurry is delivered to it in mixer by described storage container simultaneously thus, keeps the catalyst slurry of described dilution in described mixer,
Catalyst slurry in the described storage container of-optional further dilution, and
-by means of the pumping equipment (5) that is arranged in each pipeline (4),, described catalyst slurry is pumped to described polymer reactor (1) from described mixer (3) with controlled flow velocity via one or more of pipelines (4).
16. the method for claim 15 is used to optimize the polymer reactor (1) that catalyst slurry is supplied to preparation bimodal polyethylene in it.
17. claim 15 or 16 described methods, it is 0.1-10 weight % that wherein said catalyst slurry is diluted to concentration with hydrocarbon diluent.
18. each described method among the claim 15-17, it comprises: with the flow velocity of controlling by the ratio of diluent and catalyst in the control mixer (3), carry described catalyst slurry from described storage container (2) to mixer (3).
19. each described method among the claim 15-18 further comprises: before described catalyst slurry is injected described reactor, the co-catalyst of appropriate amount is contacted with catalyst slurry.
20. the described method of claim 19, it comprises makes co-catalyst contact with catalyst slurry in the pipeline (4).
21. claim 19 or 20 described methods, it comprises: the volume that increases described pipeline (4) by the part prolongs described co-catalyst and the time of contact of described catalyst slurry in pipeline (4).
22. each described method among the claim 15-21 comprises: by determining reactant in described reactor (1), the concentration of optimal ethylene is controlled the flowing velocity of described catalyst slurry from mixer (3) to polymer reactor (1).
23. each described method among the claim 15-22 comprises with suitable flow velocity via pipeline described catalyst slurry being supplied to described reactor (1) from mixer (3) continuously.
24. each described method among the claim 15-23, wherein said catalyst is a metallocene catalyst, the metallocene catalyst of preferred load.
25. each described method among the claim 15-23, wherein said catalyst is a Ziegler-Natta catalyst, and its general formula is MX n, wherein M is the transistion metal compound that is selected from the IV to Vll of family, and wherein X is a halogen, and n is the chemical valence of metal.
26. each described method among the claim 15-25, wherein said co-catalyst are optional by the organo-aluminum compound of halo, its general formula is AlR 3Perhaps AlR 2Y, wherein R is the alkyl with 1-16 carbon atom, and R is identical or different, and Y is hydrogen or halogen.
27. each described device is supplied to the application of the poly polymer reactor of preparation in it in the preparation that is used for optimizing the metallocene catalyst slurry and with it in claim 1-4,7,9-12 and 14.
28. each described device is being used for optimizing the preparation Ziegler-Natta catalyst and it is being supplied to prepare polyethylene in it, the application in the polymer reactor (1) of preferred bimodal polyethylene among claim 1-2,5-11 and the 13-14.
CNA2005800049125A 2004-02-13 2005-02-14 Method and apparatus for preparing and supplying catalyst slurry to a polymerisation reactor Pending CN1917949A (en)

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