DE1645359A1 - Process for the polymerization of olefinically unsaturated hydrocarbons in a fluidized bed - Google Patents

Description

Description of the patent application

SHEIL IMERNATIONALE RESEARCH MAATSCHAPPIJ N.V. 30 Carel van Bylandtlaan, The Hague, Fiederlande

concerning

Process for the polymerization of olefinically unsaturated hydrocarbons in a fluidized bed.

The invention relates to a catalytic method Polymerization of olefinically unsaturated hydrocarbons in the gas phase is essential Absence of liquid organic solvents or diluents, in a fluidized bed solid particles ascending gas flow.

The process is particularly important for the polymerization of CC alkenes, such as Athens, Propene and butene-1. It particularly affects the polymerization of propene. However, "olefinically unsaturated hydrocarbons" are also understood

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Compounds with more than one unsaturated bond, such as butadiene and other conjugated or non-conjugated dienes. In this description and in the claims, the terms are understood "polymerize, polymerization or polymer" also copolymerize, copolymerization or copolymer. The state of flow, the fluidized bed and the manner and manner in which these are obtained are described in the brit. Patent 666,529 described in detail. As is known, fluidized beds have the advantage of being more uniform Reaction conditions and easy heat dissipation.

In the process according to the invention, the polymerization is carried out in a fluidized bed carried out by particles of polymer previously formed from the hydrocarbon or hydrocarbons, whose polymerization is sought was obtained. The fluidized bed also contains the polymerization catalyst. The catalyst can be in polymer particles and / or in separate particles which are associated with the polymer particles are mixed, be present. The 3-gas stream flowing through the fluidized bed from bottom to top consists entirely or partially of the hydrocarbon or hydrocarbons to be polymerized.

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164535 lbs

In the method according to the invention, the speed of the ascending gas stream is ^ 5 cm / sec. and those in the flowing state During the polymerization, polymer particles are exposed to a stronger turbulence than those which would be caused exclusively by the rising gas flow. The additional vortex is created by the simultaneous use of moving parts. One preferably uses solid catalysts.

The linear speed in cm / sec. of the gas flow in the fluidized bed is the value that is obtained by dividing the amount of gas supplied in cnr / sec by the surface area of the horizontal

2 valley cross section of the empty reaction zone in cm.

It has been found that when additional turbulence is generated by moving parts, satisfactory Flow and polymerization conditions are possible, even at gas velocities below 5 cm / sec.

The method according to the invention is preferably carried out at a gas velocity below 4 cm / sec. carried out. The creation of an excess turbulence by moving parts in the 7 ^»r irbelschicht slept socvar the licglichkeit of operating at gas velocities between 0.1 and 2 cm / sec. a.

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The advantage of these low grass speeds is that much less or at all no solid particles are entrained with the grass stream from the reactor. As a result, the use of cyclones or other separators are often not necessary. The loss of solid particles from the reactor by leaching with the gas stream is also a result regulated ,. by the height of the ', Yirb el layer low set v / ird, what at slow jasgeschätze is easy to get to. A height: diameter ratio of the fluidized bed is preferably used ^ 1 i 1 at.

The additional turbulence can be achieved in various ways with the help of moving parts achieved v / earth. In the Hegel the additional turbulence is caused by stirring devices in the fluidized bed generated. However, it is very possible to use other moving parts instead of stirring arrangements, such as those that can cause the reactor or its parts to vibrate; how for example vibrators which are brought into contact with the reactor from the outside, preferably at the level of the bottom of the fluidized bed, so that the vibrations are perpendicular to the direction of the gas flow be transmitted.

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In the method according to the invention, the additional vortexing with the aid of stirring devices generated, they preferably rotate at peripheral speeds of 20-300 cm / sec. When the diameter of the stirrer changes, the circumferential speed of the stirrer becomes the greatest Peripheral speed assumed. Peripheral speeds between 50 and 50 are most preferred 200 cm / sec.

Various types of stirring devices are contemplated. Satisfactory results will be for example achieved with paddle stirrers, but the best results are obtained with reactors which with gate stirrers, especially those without a center Are equipped.

Without exception, stirring arrangements are most effective when they have a wiping effect on the bottom (which usually a sieve plate) and / or have on the ascending wall of the reactor, which means that the distance between the lower edge of the stirrer and the bottom of the reactor is very small and that the diameter of the stirrer is only slightly smaller than the inner diameter of the reactor.

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As a rule, stereo-specific catalysts are used in the process according to the invention, which can also be on carriers. Catalysts are particularly useful for the purpose of the invention of the brick type very suitable. Especially catalysts made from one or more trihalides formed by titanium and / or vanadium and one or more aluminum alkyl compounds, show satisfactory activity. It is preferred to choose a catalyst composed of an aluminum dialkyl chloride and a titanium trichloride or a mixed crystal thereof with aluminum trichloride is. The titanium trichloride can then occur in various modifications, but are used one for the production of polymers from dT-alkenes preferably the JT, £ or (5 "-IOrm. In the .cegel the titanium trichloride preferably from titanium tetrachloride by reduction with an aluminum alkyl compound, metallic aluminum or hydrogen produced at elevated temperatures.

The inventive method can be carried out very well using catalysts or one or more catalyst components previously in the presence of liquid organic diluents and / or solvents (but in the absence of

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ORIGINAL INSPECT »

1845359

polymerizing hydrocarbons) if the liquid organic diluents and / or solvents have been completely

before

or essentially bringing the catalysts together or catalyst components are removed with the I.'onomeren.

The catalysts or one or more of the catalyst components are preferably brought along There are monomers in the form of monomers with solid polymer particles together. These Gfe.-iische can through Mix the catalyst or the catalyst components with these polymer particles or by preparing the catalyst or the catalyst components have been obtained in the presence of these polymer particles. It is desirable at the beginning of the Process solid polymer particles of relatively large average size ie *, for example from 75-200 / U and a low percentage of very small and very large particles.

The preparation of mixtures of polymer particles with the catalysts or with catalyst forming Components is also preferably carried out in a flow layer. 'o during the Uisch process the affected particles x with the help of an ascending inert stream of gas, in Hegel nitrogen, in one

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BATH ORIGINAL

Maintained flowing state. In this case too, it can be desirable to use a gas velocity below 5 cm / sec. to apply, and to expose the solid particles in the flow state to an additional turbulence by moving parts, especially Hühranrichtungen.

The method according to the invention can occasionally or be carried out continuously.

In continuous processes it is important that the preparation of the catalyst / polymer mixture in an inert gas stream on the one hand and the polymerization on the other hand carried out in separate rooms will.

The polymerization temperature is usually selected from 0 to 130 ⁰ C. As a rule, ma: ITormal pressure or moderately increased pressure (1-50 ata) is used.

It was found that the additional fluidization, in the presence of which the polymerization was carried out is the comminution of the growing polymer particles after they have reached a certain size causing smaller particles. There are hardly any

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if at all, so small that can be carried away with the gas flow Particle. In this way, the average particle size becomes in the desired range while preventing agglomeration and, as a result, clogging of the reactants.

In order to compensate for any losses of volatile catalyst-forming components, for example Al (GpHj-) 9Cl, small amounts of these compounds in solution or in gas form - either intermittently or continuously - are fed to the polymerization reactor during polymerization. G-ewünschtenfalls the entire necessary for catalyst formation amount of Al (C ₂ H c) ₂ ⁰ I can ^the reactor are separated and fed in gaseous form. Al (C ₂ Hc) ₂ Cl gas can be introduced into the polymerization reactor, for example, in such a way that the gaseous hydrocarbon to be polymerized is previously passed through liquid Al (C ₂ H ₅ ) ₂ C1.

example 1

Propene was polymerized in a fluidized bed in a vertical reactor with an inside diameter 10 cm and a height of 40 cm. The reactor was provided with 1. a number of temperature measuring points, which are at different heights of the vertebral horns

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located »2. a bottom sieve plate for distribution the ascending gas flow, the amount of which is determined per unit of time with the help of Hotadureh flow meters " 7 / urde, 3. a reflux condenser, which was installed on Reactor on the 7th scale. was appropriate that the condensing liquid not along the '.Yandung could flow back, but rather dripped into the vortex bed, 4. a paddle stirrer with five on top of each other arranged wings, which are distributed over a height of £ 12 cm above the sieve plate and in one Y / angles were arranged at 90 ° to each other; all wings were up to 2 mm away from the wall, while the distance zv / isohen the floor de ": lower Wing and the sieve plate was 1.5 microns; consequently the stirrer could have a wiping effect on the Yandung and the sieve plate during the polymerization exercise, 5 an external heating coil, 6. a device for charging the catalyst suspension, which ended above the middle part of the fluidized bed and was flushed with a solvent 7. a feeding device, which is also above the middle part of the fluidized bed and used the necessary, for adding a liquid catalyst-forming component 8. an outlet which was connected to the edge of the sieve plate via an opening.

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The door was made with 1 pound 3 g of dry polypropylene powder. a -luruh-average particle size etv.'a ICC / a and eiK-sr eradicate particle size distribution. The polymer was then washed for 45 min at SC ⁰ C with nitrogen while stirring. the

r envelope was about 1 ■ \ - cm / sec while the linear speed :; ea through flowing nitrogen to 1.3 cm / sec. set was.

To eliminate the harmful effects of '.Yasser and Sauer-F'cff, the. Polymers 5 mmol ir. N ^ hexane dissolved Aiuminiusidiäthylchlorid η -AE- it help? R ^ Sinspeisun svorriciitur.g zubegeben for the liquid kata l ^ _t -3atorbildende Koaconente. The nitrogen and propene had previously been carefully freed from traces of water and oxygen.

The catalyst suspension was prepared in a separate vessel by mixing, with stirring, a solution of aluminum diethylchloride in η-hexane and a suspension of mixed crystals of litantrichloride with aluminum trichloride in a mixture of isooctane and η-hexane. The suspension of the mixed crystals was obtained by reacting titanium tetrachloride with Aluminiumtriäthyi in isooctane at 16O ⁰ C before

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bad original

in a molar ratio of 3 s 1 and by diluting the resulting suspension with η-hexane. The η-hexane and isooctane were first carefully freed from oxygen, aromatic components and water. 10 ml portions of the catalyst suspension were fed to the reactor in the manner that was present on 100 grams of polymer about 8 mmol TiCl, and 40 mmol of Al (C ₂ H c) ⁰¹ _2. During the addition of the proportions of the catalyst

A pension, the stirrer was stopped to prevent the catalyst from being thrown against the reactor wall and parts of the stirrer. Loss of Al (C ₂ Hc) ₂ Cl was prevented by the reflux condenser. Stirring was resumed after each addition and the diluent was completely evaporated before the next portion was added. The addition of the units was controlled so that the fluidized bed temperature did not drop below 60 ^0C. Even after the last portion of the catalyst suspension had been added, the entire

^ Diluent evaporated from the reactor. Evaporation s de-diluent was made in each case by stripping with nitrogen at 8O ⁰ C and reflux condenser is parked. The withdrawn solvent was recovered by condensation, and then carried along and corified Al (C ₂ Hc) ₂ Ol rendered harmless by adding ethanol *

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The discharged gas was washed with water and then passed through a wet gas meter. All Storage vessels were kept under 0.012 atmospheric nitrogen.

Polymerization was then initiated by shutting off all of the ascending nitrogen flow The reflux condenser was replaced by a propene stream, a speed of 1.3 cm / sec. and a peripheral speed of 150 cm / sec. upright was obtained.

The rate of polymerization was followed by examining the difference between the gas streams introduced and discharged as well as the heat of reaction. The polymerization temperature was about 8O ⁰ C. The average fluidized bed height was

kept almost constant at about 7.5 cm by temporarily removing polymer from the reactor. As soon as the reaction rate has reached a level corresponding to a polymer production of 6 g / mmol TiCl- * Value fell, the propene introduction was interrupted, the stirrer stopped and a fresh amount of Catalyst suspension introduced into the reactor, whereupon the stirrer again at the same peripheral speed was employed. After the supplied diluent with the reflux turned off ^

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had evaporated cooler, the reflux cooler became put into action again and introduced propene at the same 3-speed as before. From the The beginning of the polymerization at v / are furthermore every half hour 5 ml.-ol in turn dissolved in n-rlexan Al (CpHc) OCl added dropwise. With such a semicontinuous procedure, the polymerization was continued for 78.5 hours without any 3 faults occurred. After the experiment, the paddle stirrer and the iteactor wall showed some polymer deposits. 1813 g of polymer had been formed during the polymerization. Photomicrographs from samples of 10, H, 17 and 27 Ii polymer taken after the onset of polymerization, as well as of polymer with which the experiment was started, showed that the average particle size increased first and then increased to about the original value had combined.

Example 2

The experiment described in Example 1 was repeated a few times, but others were needed Velocities of the ascending gas stream and other peripheral velocities of the stirrer.

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With the exception of Experiment 4 (as is the experiment of Example 1), no experiment lasted longer than 1Ch. Further data and results are given in the following table.

Experiment gas circumferential experiment polymer disturbance- maximum tempo speed duration Particulate matter inferiority of the h in the exhaust gas was differentiated into cjn / söc. üührers, 'after 5 minutes the means cm / sec. Wt .- ^ layer zone

1 0.1 200 10 0 no <0.5 <0.5 after 4h
reactor
clogged
by Iu-
together-
agglomeration <C, 5 2 C, 2 150 10 0 no <0.5 1.0 no <0.5 3 1.3 300 1 2 Vortex-> 5
bildgin
the flow
layer 2.5 no 2.0 4th 1.3 150 0 no no 5 1.3 50 10 0 no 6th 1.3 20th 10 0 no 7th 1.3 0 4th 0 8th 2 150 10 0.5 9 2 '150 2 3.0 10 A. 20th 2 2.8

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Example 3

The experiment described in Example 1 was repeated, However, instead of a paddle ™ stirrer, a gate stirrer without a central shaft was used Reactor contained no learperaturmesainstruniente · During During the polymerization, the gate stirrer had a wiping effect on the reactor wall and the bottom sieve plate the end. The results obtained were almost identical to those of Example 1.! However showed the gate stirrer and the reactor wall At the end of the experiment hardly any polymer deposits "

Example 4 '

Experiment 3 was repeated, but the reactor had no stirrer, instead it was vibrated from the outside 2 mm above the bottom sieve plate with the aid of a vibrating machine perpendicular to the gas flow. The experiment was continued for 10 hours without any disturbances occurring 225 g of polymer were formed.

Example 5

The experiment of Example 3 was repeated by but work was carried out continuously for this purpose

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the mixed TiCla / AlCl ^ -crystallisate old the Ausgarigöpolymeiin was mixed in a separate fluidized bed, which was agitated with a saturation errührer without central force. Nitrogen was used as the ascending gas flow the circumferential transparency of the stirrer and the speed of the ascending gas stream in the fluidized bed were the same as in the turbulent bed . Polymerization reactor.

The mixture of mixed crystal was carried out! sat unä polymer in the polymerization reactor in a flowing state. The test was continued for 60 hours without disturbance, after which 1410 g were formed Polyiueres determined. Again, none were noteworthy Polymer fertilizer, stir on the gate and found on the Seaktor wall.

Claims

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Claims (11)

DR.ING. F. WUBSTHOFK '8 MORCBKH 8 DIPL.ING.G.PÜLS »ffl' SCBWXIOKRBTBAMtXt DR.E.V.PECHMANN / 9" now «» βίοι PlTENTANWlLTE TaLBaSAMMADaB (BKl PBOTMOTPATMT patent claims 1. Process for the polymerization of gaseous Vixlefinically unsaturated hydrocarbons in substantial absence of liquid organic solvents or diluents, characterized that the polymerization in a with a speed of less than 5 cm / sec. through a fluidized bed of solid particles of polymer previously obtained from these hydrocarbons an ascending gas stream, with the polymer particles contain a polymerization catalyst and / or with particles of a polymerization catalyst are mixed and one stronger than that produced by the ascending gas flow alone Turbulence will be exposed, and being the additional Turbulence is caused by simultaneous use of moving parts. 2. The method of claim 1, characterized geke η η-lines, DAF is a G-asgeschv / indigkeit in, the fluidized bed ^ 4 cm / sec. , preferably between 0.1 - 2 cm / sec. applies. 009839/2033 3 · Method according to claim 1 or 2, characterized marked that one Fluidized bed with a height: diameter ratio ^ 1t1 applies. 4. The method according to claim 1-3, characterized characterized in that stirring devices are used in the reaction zone, which are preferably Rotate with a circumferential speed of 20-300 cm / sec, in particular 50-200 em / sec. 5. The method according to claim 4, characterized in that Satterrüher used, which preferably has a wiping effect on the floor and / or the ascending V / andungen des lieactor exercise. 6. The method according to claim 1 -3 »characterized in that the reactor or the parts of which are set in vibration. 7. The method according to claim 1-6, characterized in DA3 is a counter-catalyst used, the compounds of one or more titanium and / or Variadiumtrihalogeniden and one or mehrei'en Aluminiumalky!, Preferably 009839/2033 - y- from e titanium trichloride, or a mixed one Crystals of titanium trichloride with aluminum trichloride, and an aluminum dialkyl chloride. 8. The method according to claim 71, characterized in that the catalysts or one or more catalyst components beforehand in the presence of liquid organic. Dilution and / or solvents, but in the absence of polymerizing hydrocarbons prepared and before being brought into contact with the monomers of the organic diluents and / or solvents completely or essentially completely freed have been. 9. The method according to claim 8, characterized in that the mixtures of Catalysts or catalyst-forming components with solid polymer particles also in a fluidized bed at a gas velocity of ^ * 5 cm / sec. and additional Swirling of the solid particles with the help of movable ones Parts, preferably stirrers, have been made. ■ 009839/2033 10. The method according to claim 1-9 »thereby
characterized in that the preparation of the Gfemischs the catalyst and / or one or more katalysa.torbildender components with the solid polymer particles and the polymerization in
separate rooms and preferably carried out continuously. 11. The method according to claim 1-10, characterized
characterized in that the olefinically unsaturated hydrocarbons used are CC alkenes, preferably propene. 0 0 9839/2033