GB1572572A – Autorefrigeration polymerisation process and apparatus
– Google Patents
GB1572572A – Autorefrigeration polymerisation process and apparatus
– Google Patents
Autorefrigeration polymerisation process and apparatus
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Publication number
GB1572572A
GB1572572A
GB1690/77A
GB169077A
GB1572572A
GB 1572572 A
GB1572572 A
GB 1572572A
GB 1690/77 A
GB1690/77 A
GB 1690/77A
GB 169077 A
GB169077 A
GB 169077A
GB 1572572 A
GB1572572 A
GB 1572572A
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Prior art keywords
reactor
microns
diluent
spray
solvent
Prior art date
1976-02-10
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GB1690/77A
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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1976-02-10
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1977-01-17
Publication date
1980-07-30
1977-01-17
Application filed by Exxon Research and Engineering Co
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Exxon Research and Engineering Co
1980-07-30
Publication of GB1572572A
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patent/GB1572572A/en
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legal-status
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Classifications
C—CHEMISTRY; METALLURGY
C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
C23F15/00—Other methods of preventing corrosion or incrustation
C23F15/005—Inhibiting incrustation
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
B01J19/0006—Controlling or regulating processes
B01J19/0013—Controlling the temperature of the process
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
B01J19/18—Stationary reactors having moving elements inside
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
C08F2/00—Processes of polymerisation
C08F2/04—Polymerisation in solution
C08F2/06—Organic solvent
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
B01J2219/00049—Controlling or regulating processes
B01J2219/00051—Controlling the temperature
B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
B01J2219/00108—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
B01J2219/00049—Controlling or regulating processes
B01J2219/00051—Controlling the temperature
B01J2219/00121—Controlling the temperature by direct heating or cooling
B01J2219/0013—Controlling the temperature by direct heating or cooling by condensation of reactants
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
B01J2219/18—Details relating to the spatial orientation of the reactor
B01J2219/185—Details relating to the spatial orientation of the reactor vertical
Description
PATENT SPECIFICATION
( 11) e> ( 21) Application No 1690177 ( 22) Filed 17 Jan 1977 i ( 31) Convention Application No.
11) 656983 ( 32) Filed 10 Feb 1976 inr C ( 33) United States of America (US) t Z ( 44) Complete Specification published MJ I Fy-i 9 RI
Ij T ( 51) INT CL 3 C 08 F 10/00 ( 52) Index at acceptance C 3 P LA ( 72) Inventors STUART BUTLER SMITH JAMES JOHN McALPIN JOSE MANUEL ANGEL PERUYERO RONALD LEWIS HAZELTON EDWARD FRANKLIN UPCHIJRCH ( 54) AUTOREFRIGERATION POLYMERIZATION PROCESS AND APPARATUS ( 71) We, EXXON RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Linden, New Jersey, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The present invention relates to an autorefrigeration process and apparatus for the preparation of C 2 to C 8 of alpha-olefin polymers More particularly the present invention relates to an improvement in the process of autorefrigeration which reduces fouling In one aspect the invention relates to novel apparatus for use in autorefrigeration.
Autorefrigeration generally and in this invention relates to the vaporization of solventdiluent medium from a liquid phase reaction thereby removing exothermic heat of reaction and maintaining a substantially constant temperature in the medium remaining in solurecovered, for example in a condenser and recovered solvent-diluent is returned to the tion The vaporized solvent diluent is usually reactor.
There are a number of embodiments relating to autorefrigeration In some embodiments, the solvent-diluent is a single material such as toluene, in other embodiments the solvent-diluent is a constant boiling azeotrope such as benzene-cyclohexane In other reactions the solvent-diluent which is vaporized, recovered, condensed, and returned ‘to the reactor, is either the reactant or one of the reactants in the system This latter embodiment is of particular interest in regard to the polymerization of alphaolefiris Ii any autorefrigeration, temperature control requires a vapor space in the reaction vessel into which the vaporized solventdiluent medium expands One of the common difficulties in autorefrigeration has been the fouling of the reactor at the vapor-liquid interface, in the case of the polymerization reaction, and also the fouling of the condenser because of the entrained material 50 carried overhead with the vaporized solventdiluent.
It is a feature of the present invention that autorefrigeration reactions carried on according hereto, are able to be carried out 55 for periods substantially longer than the prior art method and processes, before fouling requires the shut down and clean up of the reactor and related equipment.
It is a particular feature of the present 60 invention that a particular method of returning the recovered and cooled solvent-diluent to the reactor and to the reaction medium has been discovered, which result in substantially reduced fouling of the system 65 The invention will be better understood from the following description taken with the accompanying drawings wherein Fig 1 is a graph showing the separation efficiency of entrained particles according to 70 the present invention for one set of reactor conditions.
Fig 2 is a graph showing the separation efficiency of entrained particles according to the present invention for an alternative 75 set of reactor conditions.
Fig 3 is a graph showing the separation efficiency of entrained particles according to the present invention for an alternative set of reactor conditions 80 Fig 4 is a graph showing the separation efficiency of entrained particles according to the present invention for an alternative set of reactor conditions.
Fig 5 is a graph showing the separation 85 efficiency of entrained particles according to the present invention for an alternative set of reactor conditions.
Fig 6 is a schematic representation of an autorefrigeration polymerization system em 90 1 572 572 1 572 572 ploying the present invention.
Briefly stated, the present invention is an improvement in the autorefrigeration polymerisation reaction of alpha-olefins to produce polymers in a reaction zone comprising reacting one or more ( 2 to C 8 alpha-olefins at a temperature in the range of 20 to 80 WC in the presence of a catalyst in a solvent-diluent in liquid phase to produce an alpha-olefin polymer, vaporizing a portion of said solvent-diluent from said liquid phase, recovering said solvent-diluent, condensing said solvent-diluent and returning a portion of said solvent-diluent to said reaction zone wherein the improvement comprises returning said condensed solventdiluent into said reaction zone as a spray having a drop average particle size of less than 1000 microns.
Preferably the drop size of the spray is less than 600 microns and greater than 200 microns, with a preferred size of said spray particles being 225 to 300 microns average diameter It has been discovered that by using a spray as defined hereinabove a substantial amount of the entrained particles in the vaporous solvent-diluent which caused the fouling on the walls of the reactor and fouling in the condenser, is removed from the vapor and returned to the reaction medium The 1000 microns particle size is a critical limitation since it has been found that the average diameter of the entrained polymer particles, range between 3 and 15 microns The critical range described here is effective to remove entrained particles of microns and larger, which represents the major amount, i e, over 50 % by weight of the entrained material in the vaporous solvent-diluent By removing this substantial amount of entrained solid materials in the vapor and causing it to fall back into the reaction medium, and by washing the walls of the reactor with the sprayed solventdiluent, both the reactor fouling at the liquid vapor interface is substantially reduced as is the fouling in the overhead condensors It has been observed that the reaction may be carried on under these conditions for periods up to 6 months as compared to 1 to 2 months under the prior art not employing this invention.
The solvent-diluent may very conveniently be a reactant, and for example in the case of the preparation of polypropylene by an autorefrigeration process, the reaction may be carried out in a bulk reaction wherein the monomer propylene is both the solvent-diluent and reactant.
One aspect of the present invention is an apparatus for carrying out autorefrigeration polymerization, reactions comprising a reactor adapted to contain a liquid reaction phase, means to remove a vaporous overhead from said reactor, means to condense said vaporous overhead, and means to re turn said vaporous overhead to said reactor at a point above the liquid reaction phase in said reactor, said means for returning said condensed vaporous overhead compris 70 ing a plurality of nozzles located in said reactor, said nozzles being above said liquid phase and intermediate the liquid phase and said means for removing said vaporous overhead, said nozzles being adapted to return 75 said condensed and-cooled overhead to said reactor as a spray having an average drop particle size of less than 1000 microns The apparatus may additionally be equipped with means for adding additional reactants 80 and solvents, and means for removing a product stream therefrom containing a polymerized material.
Although the present invention will be described in detail in application to the 85 autorefrigeration, bulk polymerization of propylene to produce polypropylene, the invention is quite satisfactory for the preparation of other olefins in bulk either to produce homopolymers, or in combinations of mono 90 mers to produce various copolymers and terpolymers In a preferred embodiment the solvent-diluent is unreacted polymerization monomer, e g propylene It is of course appreciated that the solvent-diluent need not 95 be a reactant monomer, in order for the advantages of the present invention to be employed in an autorefrigeration reaction In addition to the polymerization of propylene, the present process can be applied to 100 the polymerization of other olefins such as ethylene, butene-1, hexene-1, diolefins and vinyl aromatics such as styrene, alphamethyl styrene, halo-olefins and mixtures of these monomers 105 The autorefrigeration process as described herein may be employed to produce polyolefins such as polymers of mono-alpha olefins, which comprise from 2 to 8 carbon atoms, for example, polyethylene, polypropy 110 lene, polybutene, polyisobutylenes, poly ( 4-methylpentene-1), and copolymers of these various alpha-olefins.
Olefin-vinyl copolymers which may be prepared by the present autorefrigeration 115 process include ethylene-vinyl acetate, ethylene-vinyl propionate, ethylene vinyl isobutyrate, ethylene-vinyl alcohol, ethylene-methyl acrylate, and the like Olefin-allyl copolymers include ethylene allyl alcohol, 120 ethylene allyl acetate, ethylene-allyl acetone, ethylene-allyl benzene, ethylene-allyl ether, and the like.
Although the catalyst, and the particular specific processes of polymerization are in 125 themselves not a part of the present invention, they are set forth here in order to provide an indication of the scope of the present invention.
The catalyst is normally prepared from a 130 1 572 572 transition metal compound, preferably a halide, and a reducing component consisting normally of aluminum metal or a metal alkyl compound Representative of the transition metal compounds used in a metal selected from Groups 4 b, 5 b, and 6 b of the Periodic System Included in the preferred species are the titanium halides, for example, titanium tetrachloride, titanium trichloride, and titanium dichloride, and mixtures thereof Other metal compounds such as zirconium tetrahalide and hafnium tetrachloride, vanadium chloride, chromium chloride, and tungsten chloride are especially useful Still other transition metal halides containing halogens selected from the group consisting of bromine, iodine, chlorine, and in certain instances fluorine can also be used.
The reducing component of the catalyst composition may be any of a variety of reducing agents Most common among the reducing agents are the organometallic compounds such as triethyl aluminum, aluminum diethyl chloride, aluminum ethyl dichloride, aluminum diethyl hydride, aluminum triisobutyl, aluminum triisopropyl, and related compounds.
Many other reducing agents such as lithium aluminum hydride, zinc ethyl hydride, and the like are described in the literature as useful reducing agents and can also be used These catalysts are all of the now well known “Ziegler” variety.
Certain Ziegler catalysts, or more particularly certain modified Ziegler catalysts, have been found to be especially useful for polymerizing alpha-olefins For example, a titanium trichloride catalyst modified with aluminum chloride having the formula, Ti C 3 1/3 A 1 C 13 Normally, this modified Ziegler catalyst is activated with a metal alkyl such as an aluminum alkyl, and preferably with an aluminum alkyl halide having the structural formula, RA 1 X or R 3 A Il X,, wherein R is an alkyl radical containing 1 to 12 carbon atoms or a phenyl or benzyl radical, and X is a halogen atom selected from chlorine, bromine or iodine.
A variety of monomers may be polymerized with the Ziegler type catalysts Any unsaturated hydrocarbon corresponding to the general formula R-CH=CH 2, wherein R is selected from an alkyl radical having from one to six carbon atoms Examples of specific unsaturated hydrocarbons which can be polymerized include propylene, butene, isobutylene, pentene, isoamylene, hexene, isohexenes, heptene, isoheptenes, octene, and isooctenes.
The preferred catalyst composition for the Handbook of Chemistry and Physics, The Chemical Rubber Co, Cleveland, Ohio, 45th Edition, 1964,; B-2.
polymerization of propylene comprises a modified titanium trichloride having the structural formula, Ti Clb-1/3 A 1 C 13, activated with diethyl aluminum chloride Weight ratios of diethyl aluminum chloride and 70 titanium trichloride of between 0 3:1 and 6:1 may be advantageously used The presence of an alkali metal halide in an amount of between 0 5 to 10 mols of an alkali metal halide per mol of reduced titanium tetra 75 halide, and preferably a mol ratio of from 0.8 to 5 mole of an alkali metal halide, such as sodium chloride, per mol of reduced titanium tetrahalide can be used for improving catalyst activity 80 The monomers may be polymerized at moderate temperatures and pressures with the Ziegler type catalysts described above, generally at temperatures of O C to 150 C, with temperatures on the order of 25 C to 85 C being particularly useful A solvent such as a paraffin or cycloparaffin having 3 to 12 carbon atoms, may be employed for the polymerizations; however, the olefin monomer is frequently used for this purpose 90 The polymerizations are preferably conducted under conditions that exclude atmospheric impurities such as moisture, oxygen and the like.
The pressure ranges from about atmos 95 pheric pressure to about several atmospheres, such as 20 or more atmospheres, with pressures in excess of about 500 psi rarely being employed.
After the polymer has been produced, 100 the catalyst may be deactivated by contacting the polymeric reaction mixture with a material which reacts with and deactivates the catalyst Such materials include, for example, lower alcohols, acetone and water 105 In addition to the recycle solventdiluent, fresh solvent-diluent as well as fresh reactants, if the solventdiluent is not a reactant, may be added to the reactor in order to maintain the reaction 110 and volume therein at a constant level, with the addition of fresh material being sufficient to offset at least a substantial portion of the exothermic heat of reaction and to permit the attainment commonly of a substan 115 tially isothermal reaction, i e, the temperature of the charge and the effluent from the reactor may fall within the same range; and commonly the reactor outlet temperature may be 20 to 90 C for example around 120 C The fresh reactants may be utilized at essentially the same temperature range e.g about 30 C, with the recovered and recycled solvent-diluent being appropriately in the same range e g, 20 C to 70 C or 125 C thereby not requiring that fresh feed be added at the usual low temperatures of -20 C to -50 C, which would be required in non-autorefrigeration processes From the practical point of view the reaction may be 130 1 572 572 considered as adiabatic, in that no external heating or cooling will normally be required.
These are considerations that are also well known in regard to the art of autorefrigeration, and these are commonly adjusted according to thermodynamic considerations and actual observation and operation of the reactors.
EXAMPLES
To exemplify the present invention, studies were undertaken employing propylene polymerization to produce polypropylene using a Ziegler type catalyst with the main variables under consideration being the distance of the nozzles above the liquidvapor interface, i e, 5, 10 and 15 feet, the spray drop diameter, 100 to 200 microns, the liquid injection rate 2 to 700 gallons per minute per 1000 cubic feet of vapor and entrained particle diameter of 3-15 microns.
The results of these studies determining the separation efficiency of the spray size versus the particle size of the entrained polypropylene all establish that in order to remove the 5 micron entrained solid particle even in view of the variation of the tower height, i.e, height of nozzle above the interface, and the liquid injection rate, substantially the same size of spray particle is required.
This is shown in Figs 1-5 Hence, it is seen that the spray droplet size needed is a function of the entrained solid particle size.
The conditions represented in Figs 1-5 are:
Fig 1:
Nozzles 15 feet above liquid-vapor interface, propylene injection rate through nozzles, 50 gallons per 1000 cubic feet of vapor ( 27 1 gpm) Fig 2:
Nozzles 15 feet above liquid-vapor interface, propylene injection rate through nozzles, 100 gallons per 1000 cubic feet of vapor ( 54 2 gpm).
Fig 3:
Nozzles 5 feet above liquid-vapor interface, propylene injection rate through nozzles, 100 gallons per 1000 cubic feet of vapor ( 54 2 gpm).
Fig 4:
Nozzles 15 feet above liquid-vapor interface, propylene injection rate through nozzles, 200 gallons per 1000 cubic feet of vapor ( 109 gpm).
Fig 5:
Nozzles 15 feet above liquid-vapor interface, propylene injection rate through nozzles, 700 gallons per 1000 cubic feet of vapor ( 380 gpm).
The size of the entrained particles is expressed in microns in these figures.
Fig 6 shows a flow diagram and schematic representation of the present invention Although the nozzles are a conventional item in themselves their utilization in the present environment is completely novel and unobvious.
The present invention is designed to remove a substantial portion of the entrained solid particles from, the vaporized solvent 70 diluent, however, it should be appreciated that entrained particles smaller than 5 microns will not be removed, in any event it has been found that the extended operational periods beyond that normally 75 expected for this type of reactor indicates that probably a predominant amount, well beyond 50 weight percent of the entrained particles, are being removed throughout the operation of the process 80 Referring now to Fig 6, an autorefrigerated reactor is shown The reactor 10 is fed by olefin feed through line 23 and catalyst through line 22 The monomer reactant system is agitated by agitator 13 85 driven by motor means 11 Polymer product is removed via line 15 for further processing such as drying, deashing, etc The liquid-vapor interface is indicated by line 14 The pressure in the reactor is adjusted 90 as stated before in accordance with the particular system including the temperature of the feed and the desired temperature of the reaction, to allow the vaporization of a portion of the alpha-olefin from the liquid phase 95 and its removal via line 16 to condenser 17 where the vaporous alpha-olefin monomer is condensed and returned via line 20 through pump 19 into the reactor 10 via nozzles 21 The condenser 17 is provided 100 with a vent 18.
To illustrate the operation of the present invention a propylene feed at a temperature of about 50 ‘F is fed to reactor 10 via line 23 An appropriate amount of a Ziegler type 105 catalyst is fed to the liquid propylene via line 22 with agitation The temperature of the reaction medium is about 140 ‘F and the pressure in the reactor in the vapor space is approximately 325 psig As the re 110 action proceeds under these conditions, a continuous vaporous overhead of propylene is removed via line 16 and to condenser 17 where it is condensed and leaves condenser 17 at about 950 F and hence, is returned into 115 the reactor through nozzles such as the Spraying Systems Co No 1/8 G 5, full jet spray nozzle with a nozzle pressure drop of psi which will provide a mean spray drop size of 250 microns Twenty-five of 120 these nozzles will provide approximately 55 gallons per minute of propylene recycle.
A commercial size reactor operated for commercial purposes employing this improvement was compared with a known com 125 mercial reactor not similarly adapted The prior art reactor had been observed to have an increase in pressure drop in the condenser and a heat transfer coefficient decrease in the condenser and reactor jacket, 130 1 572 572 and was operable for only one month because of a fouling of the overhead circuit.
In the apparatus according to the present invention no large change in the heat transfer coefficient of the reactor jacket was observed, however, the jacket did show a gradual decrease, which suggested some degree of fouling on the reactor wall When the reactor was opened for cleaning approximately 3 months after start-up of commercial operation, the reactor inner wall was covered with light powder about 1 centimeter thickness as far as the vapor zone was concerned, while the wall of the liquid zone was quite clean Powder build-up was observed on the spray piping, however, there was no plugging of the nozzles Powder accumulation which was anticipated from observation of the prior art commercial operation was not found in the overhead drum As for the overhead condenser, fouling was also more slight than was expected (it having been expected that the degree of fouling at the end of the 3 months operation period would at least be equal to that observed after 1 month in the prior art apparatus and procedure) There was very slight powder entrainment to the condenser, however there was no plugging of the tubes.
The reactor overhead lines were covered with thin polymer film ( 1 to 3 mm, which caused no interference) From these inspections, the reactor spray system was determined to be effective to restrain the entrainment of fine particles to the overhead condenser, but was not as effective at washing the inner walls of the reactor as might be desired In the commercial operation according to the present invention the liquid spray rate was kept at 43 gpm The number of spray nozzles in the commercial embodiment was 21 The type of nozzles is that of a Spray System Company 1/8 G 5 (equivalent) with the design of spray nozzles AP being 100 psi and spray rate of 100 gallons of 1000 cubic ft of vapor.
The reaction zone as described therein is defined generally as being that portion of the system described in Fig 6 as 10 It includes both the liquid phase portion of the reactor and vapor phase portion of the reactor 10 In constructing the reactor, it has been found that the nozzles 21, as shown in the Fig 6, should be located in the upper portion of the reactor, above the level of the liquid phase, between liquid phase and the withdrawal point for line 16 whereby the vaporized solvent-diluent is withdrawn from the system Preferably the nozzles are located in the upper 1/4 of the reactor and are situated on a plane so that the pattern of spray from each nozzle intersects that of an adjacent nozzle, and the nozzles located near the walls of the reactor 10 allow a portion of the spray to accumulate thereon and run down the wall thereby aiding in removing fouling occuring at the liquid vapor interface The nozzles are adapted to provide between 2 and 700 gallons per minute, preferably between 50 and 200 gpm 70 of spray per thousand cubic feet of vapor space in the reactor The vapor space being that portion of the reactor excluding the liquid phase portion.
The entrained particles being carried over 75 head in the vaporized solvent-diluent medium, may be characterized as a combination of polymer and catalyst, in a weight ratio which may vary from about 20 to 800:1 weight ratio of polymer:catalyst It 80 is also possible that the polymerization continues in the vapor phase, thereby resulting in even higher ratios of polymer to catalyst in the overheads The fouling in the autorefrigeration reactors results from the en 85 trained material, particularly the polymer, which plugs tubes, condensers, pumps and vents, and the like Furthermore, the foulling on the walls of the reactor can be quite substantial from the entrained particles, with go the fouling being greatest at the liquidvapor interface For example, in a commercial size reactor of approximately 20 ‘ diameter with a vaporization rate of solventdiluent of 110,600 lbs per hour, the vapor 95 carryover as solid entrained particles is about 100 weight parts per million or somewhat less in a conventional autorefrigeration system not employing the present invention By employing the present invention 100 herein, the solid particle carryover may be reduced to 30 weight parts per million or less, i e, over 50 %, by weight reduction of the solid particles in the vaporized solventdiluent according to the present invention 105 The nozzles are located so that the vaporized solvent-diluent leaving the liquid phase and passing out of the reaction zone must pass through the spray Thus the nozzles are preferably located between the 110 liquid phase in the reaction zone and the point of removal of said vaporized solventdiluent.
Claims (14)
WHAT WE CLAIM IS:-
1 An autorefrigeration process for pro 115 ducing polymers comprising reacting one or more C, to C 8 alpha-olefins in the presence of a catalyst at a temperature in the range of 20 to 80 WC in a solvent-diluent in liquid phase in a reaction zone, vaporizing a portion 120 of said solvent-diluent from the liquid phase in said reaction zone, said vaporized portion containing entrained polymer particles in the range of 3 to 15 microns, removing and condensing said solvent-diluent, and returning 125 a portion of said solvent-diluent to said reaction zone as a spray having a drop average particle size of less than 1000 microns, said vaporised solvent-diluent passing through said spray whereby over 50 weight percent 130 1 572 572 of said entrained polymer particles of 5 microns and larger are removed therefrom.
2 A process according to claim 1, wherein the average drop particle size is less than 600 microns and greater than 200 microns.
3 A process according to claim 2 wherein the average drop average particle size is from 225 to 300 microns.
4 A process according to claims 1 to 3 wherein said spray is produced by a plurality of nozzles in said reaction zone above said liquid phase.
A process according to claim 4 wherein said nozzles are located between said liquid phase and the removal point of said vaporized solvent-diluent.
6 A process according to claims 1-5 wherein said solvent-diluent is a G 2 to C 8 alpha-olefin.
7 A process according to claim 6 wherein said alpha-olefin is propylene.
8 A process according to claim 1 substantially as hereinbefore described with particular reference to the accompanying Examples.
9 Polymers of CQ-C 8 alpha-olefins whenever prepared by a process according to any of the preceding claims.
10 An apparatus for conducting autorefrigeration polymerization reactions according to claims 1-8 comprising a reactor adapted to contain a liquid reaction phase, means to remove a vaporous overhead from said reactor, means to condense said vaporous overhead, and means to return said vaporous overhead to said reactor above the liquid reaction phase 40 in said reactor, said means for returning said vaporous overhead comprising a plurality of nozzle means located in said reactor, above said liquid reaction phase and intermediate said liquid reaction phase and said 45 means for removing said vaporous overhead, said nozzle means being adapted to return said condensed overhead to said reactor as a spray of drop average particle size of less than 1000 microns 50
11 An apparatus according to claim 10 wherein said nozzle means are located in the upper one fourth of said reactor.
12 An apparatus according to claim 10 or 11 wherein said nozzle means provides 55 said spray at a rate of 2 to 700 gallons per minute per 1000 cubic feet of vapor.
13 An apparatus according to claims 10 to 12 wherein said nozzle means are adapted to provide a spray or drop average particle 60 size of greater than 200 and less than 600 microns.
14 An apparatus according to claim 13 wherein said nozzle means are adapted to provide spray of drop average particle size 65 of 225 to 300 microns.
Apparatus for the polymerization of alpha-olefins according to claim 10 substantially as described with reference to the examples 70 16 Apparatus for the polymerisation of alpha-olefins according to claim 10 substantially as hereinbefore described with reference to the accompanying Figure 6.
K J VERYARD, Suffolk Street, S W 1.
Agent for the Applicants.
Printed for Her Majesty’s Stationery Office by The Tweeddale Press Ltd, Berwick-upon-Tweed, 1980.
Published at the Patent Office, 25 Southampton Buildings London WC 2 A l AY, from which copies may be obtained.
GB1690/77A
1976-02-10
1977-01-17
Autorefrigeration polymerisation process and apparatus
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GB1572572A
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Autorefrigeration process and apparatus
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Autorefrigeration polymerisation process and apparatus
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BE851236A
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CA
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CA1059331A
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DE
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DE2703167A1
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FR
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FR2340957A1
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US4232137A
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1978-09-14
1980-11-04
Phillips Petroleum Company
Cooling an alpha-methylstyrene polymerization mass
US4214063A
(en)
*
1979-01-11
1980-07-22
Exxon Research & Engineering Co.
Autorefrigerated polymerization process
JPS56110701A
(en)
*
1980-02-07
1981-09-02
Sumitomo Chem Co Ltd
Method and apparatus for removal of heat from polymerizer
EP0661093B1
(en)
*
1993-12-28
1998-07-22
Shin-Etsu Chemical Co., Ltd.
Polymerization apparatus effective in preventing polymer scale deposition and process of producing polymer using the same
KR19990022376A
(en)
*
1995-06-07
1999-03-25
바실리오 유스타티오
Method and apparatus for preparing intermediate product by controlling conversion and temperature in sprayed liquid
FR2749014B1
(en)
*
1996-05-24
1998-07-03
Bp Chemicals Snc
OLEFIN (S) POLYMERIZATION PROCESS
JP4128220B2
(en)
*
1996-05-24
2008-07-30
ビーピー ケミカルズ リミテッド
Olefin polymerization method
US8192695B2
(en)
*
2005-05-04
2012-06-05
Fina Technology, Inc.
Reactor apparatus having reduced back mixing
US7511101B2
(en)
*
2005-05-13
2009-03-31
Fina Technology, Inc.
Plug flow reactor and polymers prepared therewith
KR102421977B1
(en)
*
2018-12-19
2022-07-18
주식회사 엘지화학
Method and apparatus for preparing aromatic vinyl compound-vinylcyan compound copolymer
KR102581118B1
(en)
2019-12-09
2023-09-20
주식회사 엘지화학
Apparatus for preparing oligomer
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1958-08-11
US3062796A
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*
1959-05-11
1962-11-06
Shell Oil Co
Production of synthetic elastomers
US3193360A
(en)
*
1961-05-31
1965-07-06
Phillips Petroleum Co
Apparatus for propylene polymerization
JPS5230539B1
(en)
*
1970-08-08
1977-08-09
IT1044367B
(en)
*
1975-08-08
1980-03-20
Anic Spa
PROCEDURE FOR THE REMOVAL OF STAINS FROM PARTS IN CONTACT WITH THE GASEOUS PHASE IN SUSPENSION VINYL CHLORIDE POLYMERIZERS
1976
1976-02-10
US
US05/656,983
patent/US4058652A/en
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Expired – Lifetime
1977
1977-01-17
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GB1690/77A
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Expired
1977-01-26
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Withdrawn
1977-02-09
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BE174773A
patent/BE851236A/en
not_active
IP Right Cessation
1977-02-09
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IT20117/77A
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active
1977-02-09
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FR7703648A
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not_active
Withdrawn
1977-02-09
CA
CA271,384A
patent/CA1059331A/en
not_active
Expired
1977-02-10
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1977-08-11
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1977-08-09
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1977-09-09
JPS5296687A
(en)
1977-08-13
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Legal Events
Date
Code
Title
Description
1980-10-15
PS
Patent sealed [section 19, patents act 1949]
1983-09-07
PCNP
Patent ceased through non-payment of renewal fee
