US3773470A - Apparatus for continuous chemical reactions - Google Patents

Apparatus for continuous chemical reactions Download PDF

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US3773470A
US3773470A US00121949A US3773470DA US3773470A US 3773470 A US3773470 A US 3773470A US 00121949 A US00121949 A US 00121949A US 3773470D A US3773470D A US 3773470DA US 3773470 A US3773470 A US 3773470A
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tube
separators
materials
point
origin
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G Rouzier
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Compagnie Generale des Etablissements Michelin SCA
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Compagnie Generale des Etablissements Michelin SCA
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    • 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
    • B01J19/1812—Tubular reactors
    • B01J19/1831—Tubular reactors spirally, concentrically or zigzag wound
    • 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
    • B01J19/1812—Tubular reactors
    • B01J19/1837—Loop-type reactors
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • 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
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • ABSTRACT A closed loop reaction tube is formed with a substantially constant interior cross section. A plurality of movable separators in the tube divide it into a plurality of separate cells. Materials for reaction are circulated through the tube in separate batches respectively confined in the cells. A plurality of reaction stations are provided at spaced locations along the tube, and at these stations the transported batches are successively [30] Foreign Application Priority Data May 2, 1967 France 67104970 acted p The tube has a Point of Origin and a minal point connected by a lock for passing the sepa- 52 US. Cl.
  • the present invention relates to chemical reactions and, more particularly, to novel and highly-effective apparatus facilitating continuous chemical reactions, particularly polymerizations or copolymerizations of olefins or diolefins.
  • reactors operating continuously and under steady-state conditions.
  • the reactor system is said to be of the continuous or open type.
  • Several reactors of this kind can be operated simultaneously, the reactors being connected in parallel, in series, or in a more complex way.
  • Open reactors operating continuously are preferred by industry, since their operation is less complicated, more economical, and better adapted for automation. However, their possibilities are more limited than those of closed or half-closed type reactors, inasmuch as the latter enable the operator to interfere at any time and to control the chemical reaction as he desires. Conditions including speed, temperature, pressure, and concentration can be changed at will; new reagents can be introduced; and all or part of the reaction products can be drawn off. It is thus possible to take into account reactional selectivity, critical operations, and the kinetics of reactions and thus to obtain an optimal progression of the desired chemical transformation. These capabilities are of particular importance in the case of complex reactions.
  • An object of the present invention is to combine the simplicity and economy of continuous or open reactors with the flexibility'and variability of the closed or semiclosed type. Another object of the invention is to facilitate the industrial manufacture of products which can be manufactured today only in the laboratory, under conditions of reproducibility and regularity difficult to obtain in the laboratory. A further object of the invention is to facilitate the manufacture of large quantities of products, especially polymers and copolymers, conforming to predetermined specifications and under conditions of automation equalling those characterizing conventional apparatus.
  • a representative apparatus in accordance with the invention for continuously carrying out chemical reactions, especially polymerizations and copolymerizations particularly of olefins or diolefins, by means acting on separate measured quantities of reacting materials contained in cells movable within a fixed tube, the cells being separated from one another by movable separators.
  • the apparatus is characterized by means causing the cells to circulate sequentially past a plurality of spaced-apart stations where the transported measured quantities are continuously acted on by means of programmed operations such as injection of products (solvents, reagents, catalysts, etc.), drawing off or recycling of products, modification of the operating conditions (especially the temperature), mixing, taking of samples, and measurement of parameters.
  • the cells always full, have a variable volume because of the moving apart or closer together of the separators.
  • the range of times within which the various operations are carried out is a function of the distance of the several stations from a point of origin.
  • the apparatus in accordance with the invention thus combines the advantages of the continuous method with those of the discontinuous method.
  • Each cell is in effect a small reactor of the closed or semi-closed type.
  • the cells circulate continuously along a circuit through which they travel sequentially: i.e., one after another. At each station of the circuit, steady-state conditions prevail. On the other hand, in each cell, conditions are transient or changing all along the circuit.
  • the reacting materials are preferably mixed at least in part prior to entering the reactor, and the reaction is then carried out in the reactor proper.
  • the concentration of a catalyst or one or another reagent may be varied in accordance with a certain rule, in order to obtain in succeeding cells polymers having different characteristics-for example, different average molecular weights.
  • Successive cells can be periodically specialized for the production of a given polymer in different molecular weights, in order to obtain by mixing a batch of a polymer having a molecular weight distribution with a desired profile.
  • the apparatus in accordance with the invention is applicable in particular to the polymerization or copolymerization of monomers, especially unsaturated monomers, such as ethylene, propylene, butylene, butadiene, isoprene, styrene, and methyl methacrylate, as well as all their higher homologs and many of their derivatives including their halogen derivatives.
  • monomers especially unsaturated monomers, such as ethylene, propylene, butylene, butadiene, isoprene, styrene, and methyl methacrylate, as well as all their higher homologs and many of their derivatives including their halogen derivatives.
  • reaction methods can be used, such as polymerization in bulk, in solution, in suspension, and in emulsion.
  • conventional catalytic and initiator methods can be used.
  • the reactor in accordance with the invention comprises a tube of substantially constant cross-sectional shape and interior surface, wherein the reaction medium is caused to circulate in distinct doses partitioned off by movable separators, preferably of spherical shape.
  • the tube forms a closed circuit between a point of origin and a terminal point, which points are separated by a partition which is impervious to the reaction medium and traversed by a gate or lock facilitating the transfer of the separators from the terminal point to the point of origin, so that the separators are recycled.
  • a permanent pressure differential is established by any suitable means sufficient to keep the tube full and to assure the propulsion of the reaction medium and the separators, both substantially at equal speed, in relation to the tube, such speed preferably remaining invariable at any given point of the circuit.
  • the difference in pressure between two points is a function of the delivery rate and the viscosity of the fluid.
  • the difference in pressure between the point tors and the inner wall of the tube, and the ascending or descending slope of the tube is a function of the delivery rate and the viscosity of the fluid.
  • the difference in pressure to be established between the point of origin and the terminal point may be obtained by means of pumps which inject fluids constituting the reaction medium at the point of origin and at intermediate points and by means of a discharge valve the delivery rate of which can be regulated.
  • a discharge valve the delivery rate of which can be regulated.
  • hydrostatic pressure supplied by reservoirs placed at a higher level than the tube Preferably, the discharge valve is regulated in relation to the intake pressure of the tubular reactor so as to maintain the pressure differential constant and to stabilize the pressures and rates of flow at all points of the reactor, thereby facilitating the establishment of a steady-state flow at each point.
  • the circuit formed by the tube is designed in such a manner as to spread the load losses and the progressive drop of pressure over a great length in relation to the diameter of the tube, so that on either side of each separator and in the vicinity of it the pressures can be considered as practically equal.
  • the tubular reactor is constructed of tubular elements which are arranged almost horizontally, and the separators have a density which is close to that of the reaction medium.
  • the purpose of this provision is to avoid subjecting the separators and the reaction fluid to different effects of gravity.
  • a too-steep incline of the tube may cause the separators to move through the tube at a speed different from the speed of the reaction fluid.
  • the rectilinear elements of the tube can be mounted to ascend at a shallow angle, whereby a more pronounced descending inclination can be given the curved elements connecting the rectilinear elements. This facilitates the passage of the separators through these curved elements.
  • a difference in levels or substantial inclinations between points near each other requires in general a compensation in form of a reduction of the clearance between the separators and the inner wall of the tube, especially if the reaction medium has a low viscosity. This is true, for example, in the vicinity of the terminal point, where the tube preferably rises again to its initial level, if the final viscosity at the end of the reaction has not substantially increased.
  • the tubular reactor consists of a bundle of tubular elements which are rectilinear and have the same length and are arranged almost horizontally and in parallel in superimposed layers at slightly different levels and are connected by semicircular knees.
  • Each tube is enclosed in a second cover which is heat-insulated and wherein a fluid serving for heating or cooling is circulated.
  • the various injections or interventions preferably take place in the connecting knees.
  • the separators have preferably a spherical shape, which enables them to roll in the tube. There is, of course, less friction for separators that roll than for those that slide. Furthermore, this facilitates passage with minimum clearance through the semicircular knees. Their density is close to the density of the reaction medium so as to render their floatability as low as possible and to eliminate zones of local contact or impact at the wall of the tube. Towards such end, one may make use of hollow spheres obtained, for example, by a welding or soldering together of hemispheres made of metal of some suitable thickness.
  • the separators can consist of any material that is chemically inert in the reaction medium. Of course, a form other than spherical may be provided without exceeding the scope of the invention: for example, a cylindrical shape which bulges out in the middle or which is provided with sealing elements such as the sealing rings of the pistons of internal combustion engines. 7
  • the clearance between the separators and the inner wall of the tube i.e., the difference between the radii of their cross sections-is preferably, but not necessarily, small: for example, ranging around one or two per cent of the inner diameter of the tube.
  • Absolute tightness is not required. The relative tightness must increase as the inclination of the tube with respect to the horizontal increases and as the speed of the reaction fluid decreases.
  • the minimum speed is about 1 to 5 cm/sec. for tube diameters ranging from to 500 mm.
  • speeds ranging from one to 10 times the diameter of the tube per second are suitable, especially if the clearance between the inner wall of the tube and the separators is approximately one to two hundredths of the inner diameter of the tube.
  • the distance between consecutive separators and thus the total number of separators present simultaneously can be varied within a wide range.
  • the invention comprises the case in which the reactor is divided into only two or a small number of compartments, it is preferable to use a large number of compartments and of separators without, however, a reduction of the length of each compartment to less than 10 times the diameter of the tube. In general, good results are obtained with compartments the length of which ranges from 10 to 200 times the diameter of the tube.
  • connection between the terminal point of the tubular reactor and the point of origin is effected by a distributor assembly comprising a tight partition through which fluid cannot pass but which the separators can transverse by means of a lock or gate.
  • the interior volume of the lock is substantially the same as that of a separator so that substantially no reaction fluid is carried along.
  • Various devices can be used to enable the separators to clear the tight partition.
  • these two cylinders can seize a separator on one side of the tight partition, carry it to the other side, and discharge it there.
  • Hydraulic jacks orany other suitable means effects the translational movements of one or both of the cylinders.
  • Another, preferred, system consists in the application of at least one of the two cylinders with its hollow base against the tight wall which has an opening the dimensions of which permit the passing of one separator. In this manner, the two cylinders secure alternatingly the tight closing and the opening for passing of the separator.
  • the reactor in accordance with the invention affords great ease of control of operations. For example, by automatic measurement in certain points of the parameters, such as temperature or concentrations, it becomes possible to cause, upstream or downstream, an increase or decrease of the flow, for example, of the thermal flux, or also of the rate of injection of a reagent.
  • FIG. 1 is a plan view of a simplified embodiment of a reactor in accordance with the invention.
  • FIG. 2 is a perspective view, partly schematic, of a preferred embodiment of a reactor in accordance with the invention.
  • FIG. 3 is a cross sectional view in the plane 3-3 of FIG. 2, the view being in the direction indicated by the arrows;
  • FIG. 4 is a longitudinal section of a portion of the apparatus of FIG. 2;
  • FIG. 5 is a longitudinal section of another portion of the apparatus of FIG. 2;
  • FIG. 6 is a detailedplan view ofa portion of the apparatus of FIG. 2 shown schematically in FIG. 2;
  • FIG. 7 is a sectional view in the plane 7-7 of FIG. 6, the view being in the direction indicated by the arrows;
  • FIG. 8 is a sectional view in the plane 8-8 of FIG. 7, the view being in the direction indicated by the arrows;
  • FIG. 9 is a sectional view in the plane 9-9 of FIG. 7, the view being in the direction indicated by the arrows;
  • FIGS. 10 to are graphs showing certain important characteristics of polymers respectively obtained in the case of Examples 1 to 6 which follow.
  • FIG. 1 illustrates somewhat diagrammatically the reactor in accordance with the invention as applied, for example, to a copolymerization of styrene and butadiene dissolved in heptane, by meansof a catalyst of the butyl lithum kind.
  • a tubular chamber 21 is connected at a point of origin 22 and a terminal point 23 to a distributor 24 including lock means.
  • the tubular chamber 21 contains a reaction medium divided into doses 25 by means of spherical separators or balls 26.
  • the tube 21 is surrounded by double covers 27 each having an intake 28 and an outflow 29 making it possible to circulate around the tube 21 a fluid regulating the temperature of the reaction medium contained in the tube 21.
  • the division into sections of the double covers 27 makes it possible to maintain different temperatures of the reaction medium at various points along its travel. A certain number of intervening stations is provided along the route and the interventions take place continuously.
  • the distributor 24 is connected to an intake 31 for fluid under pressure which may consist, for example, of the solvent containing the monomers.
  • the pressure is generated by a pump P in the intake 31.
  • the catalyst is introduced by means of a metering pump 33.
  • the mixing takes place.
  • the reaction medium is drawn from the tube 21 through a tube 34 and forced back through a tube 35 by means of a pump 36.
  • supplementary injection is provided at a point 38 by means of pump 39 introducing, for example, a catalyst or one of the monomers.
  • part of the reaction medium drawn off through a line 41 by means of a pump 42 is recycled.
  • substance is drawn off by means of a pump 44 for the purpose of control, for example, of the proportion of styrene polymerized.
  • reaction can be slowed down or speeded up by reducing or increasing the temperature between sections of the tube, so that each of the jackets 27 constitutes an additional means for intervening in the process.
  • reaction medium is discharged through line 45 which is in communication with the terminal point 23.
  • This line 45 contains a variable discharge valve V regulated by a pressure sensor S which is connected to the valve V and which senses the pressure of the reaction medium near the origin.
  • the several spherical separators 26 are carried along by the circulating reaction medium, and the separation between adjacent separators 26 increases when materi-- als for reaction are added and decreases when substance is drawn off.
  • the diameter of the balls 26 is substantially the same as the diameter of the tube 21. However, adjacent to the terminal point 23, the diameter of the tube 21 increases starting at a point 46. From there on, the tube forms a storage room for separators so as not to increase the loss of head due to the accumulation of separators.
  • the distributor 24 comprises a block traversed by a longitudinal bore 47 in which slide two pistons 48 and 49.
  • the bore 47 is in communication with the intake 31 and the point of origin 22 on the one hand and with the discharge 45 and the terminal point 23 of the tubular chamber 21 on the other.
  • the bore 47 is closed off in the middle by a tight partition 50 formed with a hole 51 the diameter of which is substantially equal to the diameter of the separators 26.
  • the bases of the pistons 48 and 49 are formed with cavities 52 and 53, respectively, which are substantially hemispherical and have a diameter substantially equal to the diameter of the separators 26.
  • the cavities 52 and 53 are surrounded by shoulders 54 and 55, respectively, adapted tightly to engage opposite sides of the partition 50.
  • the pistons 48 and 49 are provided with ejectors 56 and 57, respectively, biased by springs 58 and 59, respectively, for the purpose of ejection of the balls 26 as described below.
  • Each of the pistons 48 and 49 is able to slide in the bore 57. Their movement is controlled, for example, by hydraulic jacks (not shown).
  • the piston 48 Whenever the piston 48 is forced against the partition 50, it prevents communication through the distributor 24 between the origin 22 and terminus 23 of the tube 21.
  • a separator 26 carried along by the current, enters the bore 47.
  • the piston 49 When the piston 49 is about to be placed against the partition 50, it seizes the separator 26, taking along practically no liquid, and, as soon as it is forced against the partition 50, it in turn prevents communication through the distributor 24 between the points 22 and 23.
  • the piston 48 can move away now whereby the separator 26 is set free and carried along with the current. Seals 60 and 61 enable the pistons 48 and 49 to slide tightly in the bore 47.
  • the transfer of a separator 26 from the terminal point 23 to the point of origin 22 is controlled manually, or automatically by any suitable means including an automatic switch S operated at timed intervals or by the passage ofa separator through a given point of the circuit, e.g., the point 46.
  • FIGS. 2 to 5 show a preferred embodiment of a reactor in accordance with the invention.
  • the reactor comprises a tube assembly formed by a series of straight or rectilinear segments 70. Each tube is rounded by a double envelope 71 (FIG. 4) provided with an intake 72 and discharge 73 for the heating or cooling fluid. At each end there is installed a fixed flange 74 and a movable flange 75. Two successive straight tubes 70 are connected by a U-shaped segment or knee 80, the latter being formed with two fixed flanges 81 which are bolted to the movable flanges 75. In the flanges 81 there are provided threaded bores 82 into which are screwed either a stopper or a connection to a line and pump for injection or drawing off.
  • the tubes 70 are not on the same level in each layer.
  • a slight upward slope is provided, for example 1%, in the direction of circulation so that the knees are at different levels at each end.
  • the knees 80 are shorter than the straight segments 70, and their slopes, which are downward, are correspondingly steeper. This facilitates the passing of the balls 26 through the knees 80.
  • FIG. 2 shows the point of origin 22, the terminal point 23, the distributor 24, the main fluid intake 31, and the discharge 45.
  • the last tube 87 is the only one which shows a considerable incline and which requires inside machining with great precision so that the clearance between the inner wall and the separators is small,
  • FIG. 2 also shows the feed 32 of additional fluid as well as a point of intermediate injection 35.
  • FIGS. -6 to 9 illustrate a distributor comprising lock means which has been operated with excellent results in combination with a tubular chamber such as the one shown in FIGS. 2 to 5.
  • the distributor comprises a block formed with various transverse and longitudinal bores and one vertical bore.
  • Superimposed transverse bores 121 and 122 serve for the passage of fluids constituting the reaction medium, the bore 122 communicating with the reaction tube at the point of origin 22 and the bore 121 communicating with the reaction tube at the terminal point123.
  • the role of the distributor is to permit the transfer of the balls from the bore 121 to the bore 122 through lock means whichprevents the passage of fluid.
  • the upper bore 121 is connected to a tube 123 forming the end of the tubular reactor and to a tube 124 constituting the discharge for the fluids and connected to the discharge valve (not shown).
  • the lower bore 122 is connected to a tube 126 forming the feed 31 of the reactor and to a tube forming the start of the tubular reactor.
  • the distributor comprises furthermore two longitudinal bores 130 and 131 (FIG. 7) which are superimposed and run into the transverse bores 121 and 122, respectively, at right angles.
  • the bores slide pistons 133, 134, and 135, 136, respectively.
  • Inflatable seals 141 held by rings and connected to intakes of fluids under pressure facilitate the sliding of the pistons while preventing leakage of fluid.
  • the two pistons 133 and 135 on the one hand and 134 and 136 on the other are connected to flanges and 151, respectively, by bolts 152, and the flanges 150 and 151 themselves are connected to rods 153 and 154 of hydraulic jacks 155 and 156, respectively.
  • the pistons 133 and 134 have their bases facing each other, and each of the bases has a hemispherical cavity 157 with a diameter which is substantially equal to the diameter of a separator so that, whenever a separator 139 is held between the two pistons, a minimum quantity of liquid is enclosed in the cavity together with the separator.
  • Each of the pistons 133 and 134 is likewise equipped with an ejection system comprising an ejector 158, a spring 159,and a screw 160 which is threaded into a center thread 161.
  • the distributor has a vertical bore connecting the bores 130 and 131.
  • the bore 170 is connected to an intake tube 171 for separator washing fluid and to a tube 172 for discharge of the washing fluid.
  • the tube 172 opens into an intermediate socket 173 closed off by a stopper 174 from which extends a center rod 175 the vertical position of which is adjustable by means of a wheel 176.
  • FIG. 9 shows a transverse bore closed off by two glass plates 181 and 182 respectively mounted in frames 183 and 184 screwed to the block 120.
  • the glass plates 181 and 182 make it possible to observe what goes on in the vertical tube 170.
  • the assembly of the fixed elements constituting the distributor, including the block 120 and the jacks 155 and 156, is mounted on a fixed frame 162 consisting of angle irons which are assembled by any suitable means including bolts, rivets, welding, and soldering.
  • FIG. 8 shows the fluids kept in the reactor arrive at the distributor and travel through it by means of thetube 123, the bore 121 and the tube 124. However, the separators are stopped by the screen 137. To transfer a separator stopped by the screen 137 in the upper bore 121 to the lower bore 122, one operates the hydraulic jacks 155 and 156 (FIG. 7) to cause the pistons 133 and 134 to approach each other, whereby the spherical separator is seized by them. Thereafter, one causes their displacement in manner whereby the separator is moved to the vertical bore 170.
  • the separator is released by the jacks 155 and 156 and drops into the bore 170, being then driven by the washing fluid circulating in the tubes 171 and 172.
  • the separator is stopped by the rod 175 and seized by the pistons 135 and 136.
  • a displacing movement then guides the separator to the bore 122 (FIG. 8), whence it is carried by the fluid circulating in the tubes 126 and 125.
  • a tubular reactor such as the one described in FIGS. 2 to 9 functions with outstanding results and can be easily adapted to various polymerizations and reactions.
  • certain precautionary measures be taken during the start of operations.
  • an inert fluid for example a pure solvent or a solvent containing monomers.
  • Regulating becomes much easier if the reaction is initiated first, whereafter the distribution of the separators can be started.
  • the viscosity of the reaction medium should be all along the tube.
  • the viscosity may be much different from the viscosity of the medium in the process of reaction.
  • total rate of flow approximately 45 liters per hour
  • EXAMPLE 1 At the intake of a reactor one introduces, under a pressure of 10 kglcm 40 liters/hour of heptane and 4.6 liters/hour of butadiene.
  • graph A The molecular distribution is shown in FIG. 10, graph A.
  • graph B shows the molecular distribution of the polymers obtained under conditions as nearly as possible the same in the laboratory in flasks of 250 cm
  • graphs C and D show the molecular distribution of polymers obtained by continuous reactions in a vat using the same catalytic system and substantially the same average reaction times and doses.
  • the polymer obtained in accordance with the method of the invention is similar to a polymer prepared EXAMPLE 2
  • the butyl lithium is added at a rate of 0.04 pph, one introduces 0.10 pph of hexamethyl phosphorotriamide and mixes by suction and then forcing back at accelerated speed through a small loop by means of a centrifugal pump.
  • the pressure at intake is 8 kglcm and the temperature is 30C all along the circuit.
  • the resulting solution which is antioxidized and arrested, is recovered at the discharge.
  • the inherent viscosity is 1.65, and the Mooney plasticity of the polymer is 48.
  • the polymeric structure is as follows:
  • Graph A shows the molecular distribution of the polymer obtained.
  • Graphs B and C respectively, show the molecular distributions of the polymers obtained in a similar manner but with, respectively, 30% and 18% of styrene in the styrene-butadiene mixture in place of 23%.
  • Graph D shows the molecular distribution obtained when the separators are eliminated from the reactor, and graph E shows the molecular distribution obtained under the same conditions by means of a conventional open reactor.
  • EXAMPLE 3 The processing Example is repeated, except that the catalyst and hexamethyl phosphorotriamide (l-IMPT) are added in two batches. During the first stage, one introduces 0.013 pph butyl lithium and 0.036 pph HMPT and maintains a temperature of 35C.
  • l-IMPT hexamethyl phosphorotriamide
  • the polymer obtained has a bi-dispersed molecular distribution shown in the graph A in FIG. 12.
  • the characteristics are:
  • the copolymer obtained while having characteristics similar to those of Example 2, offers the advantage of being easier to work.
  • the first injection is at 0% conversion, i.e., in the vicinity of the origin, and consists of 0.0 l 2 pph butyl lithium and 0.036 pph l-IMPT.
  • the second injection is at 44% conversion, i.e., at a distance from the origin corresponding to 20% of the length of the reactor, and consists of 0.015 pph butyl lithium and 0.045 pph HMPT calculated on the basis of initial monomer.
  • the third injection is at 60% conversion, i.e., at a distance from the origin corresponding to 33% of the length of the reactor, and consists of 0.028 pph butyl lithium and 0.08 pph I-IMPT, calculated on the basis of the initial monomer.
  • the dwelling time is two hours, as in the other examples.
  • the pressure at the intake is 8 kg/cm.
  • the temperature is 35C between the first and the second injections, 27C between the second and the third injections, and 30C between the third injection and the point of introduction of the antioxidant and the reaction arrester.
  • the final polymer obtained has an inherent viscosity of 2.15 and a Mooney plasticity of 60. Its molecular distribution is a little wider than that of the polymer in Example 3, as shown in the graph A in FIG. 13. Although the Mooney plasticity is the same as in Example 3, the inherent viscosity is higher.
  • EXAMPLE 5 there is obtained a butadiene-styrene copolymer with a statistical distribution of the two monomers in the chains, without using a polar compound, such as tetrahydrofurane or hexamethyl phosphorotriamide.
  • a polar compound such as tetrahydrofurane or hexamethyl phosphorotriamide.
  • the average compositionof the copolymer is 22% styrene, the content of 1-2 structures is approximately 10%, and
  • the polymerization maybe continued by further additions in several stages of butadiene. In such case, the
  • EXAMPLE 6 In this example, it is the aim to influence, on the .one hand, the distribution of the monomers (butadiene and styrene) in the chains, and, on the other,-the microstructure, especially the l-2 content, as indicated in a French patent No. 1,519,743 of Feb. 20, 1967, of Societe Michelin &Cie.
  • the temperature is maintained along the entire length of the tube at 60C.
  • the copolymer which forms is not completely statistical and becomes enriched in styrene but has a low l-2 content.
  • the butadiene complement is introduced at an hourly rate of 1.28 liters.
  • the composition at successive points along the tube of the copolymer which is formed becomes progressively richer in butadiene.
  • the profile of the instantaneous compositions of the copolymers is indicated in the graphs in FIG. 15. in the same manner as in FIG. 14.
  • the full line A plots the instantaneous styrene content
  • the broken line B the mean styrene content of the copolymer formed.
  • the copolymer obtained has the following characteristics: inherent viscosity: 1.70; Mooney plasticity: 57; l-2 content: 29%; trans l-4 content: 47% vitreous transition temperature during differential thermal analysis: 54C.
  • the graphs indicate:
  • Apparatus for carrying out chemical reactions comprising reaction tube means having a point of origin and a terminal point, said tube means having a substantially constant interior cross section, a plurality of movable separator means in said tube means dividing said tube means into a plurality of separate cells, circulation means for circulating materials for reaction through said tube means in separate batches respectively confined in said cells, said point of origin and said 7 terminal point being connected by a lock for passing said separator means from said terminal point to said point of origin while preventing-passage of said materials, said materials being discharged from said tube means, and said circulating means maintaining a pressure differential along said tube means from" said point of origin to said terminal point sufficient to maintain said tube means full and to ensure the propulsion of said materials and separators thorugh said tube means at substantially the same velocity, whereby continuous chemical reactions involving successive batches of said materials occur as said materails traverse said tube means, said lock means comprising pistons formed with hemispherical cavities and said separator means comprising a plurality of spheres of the
  • said circulation means comprises an injection pump, a variable discharge valve, and means for regulating said discharge valve as a function of pressure adjacent to said point of origin.
  • said tube means comprises a plurality of straight tubular segments, each segment being mounted substantially horizontally and doubling back on adjacent segments, successive segments being connected by a U-shaped segment.
  • Apparatus according to claim 4 further comprising a plurality of reaction stations at spaced locations along said tube means where the transported batches are successively act upon and means connected to at least some of said U-shapcd segments for selectively adding materials to and withdrawing materials from said cells.
  • said separator means comprises a plurality of separators, said separators being spaced apart a distance equal to ten to two hundred times the interior diameter of said tube means.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Polymerisation Methods In General (AREA)
US00121949A 1967-05-02 1971-03-08 Apparatus for continuous chemical reactions Expired - Lifetime US3773470A (en)

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FR104970A FR1547405A (fr) 1967-05-02 1967-05-02 Procédé et réacteur pour la conduite en continu de réactions chimiques, notamment de polymérisation

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BE (1) BE714005A (xx)
CH (1) CH490113A (xx)
DK (1) DK137003B (xx)
ES (1) ES353414A1 (xx)
FR (1) FR1547405A (xx)
GB (1) GB1228831A (xx)
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595566A (en) * 1984-05-30 1986-06-17 Halliburton Company Continuous reactor design
AU626706B2 (en) * 1989-08-08 1992-08-06 Crown Berger Europe Limited Polymerisation processes and reactors
US5779994A (en) * 1995-10-16 1998-07-14 Bayer Aktiengesellschaft Tubular reactor
US6492184B1 (en) * 1998-04-03 2002-12-10 Symyx Technologies, Inc. Automated sampling methods with integral serial sample preparation for rapid characterization of polymers
US20030070988A1 (en) * 1998-04-03 2003-04-17 Miroslav Petro Rapid characterization of polymers
US20030080062A1 (en) * 2001-08-28 2003-05-01 Miroslav Petro Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with regular second-dimension sampling
US20030089663A1 (en) * 1999-04-02 2003-05-15 Miroslav Petro Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with parallel second-dimension sampling
US20060054543A1 (en) * 2004-09-03 2006-03-16 Symyx Technologies, Inc. System and method for rapid chromatography with fluid temperature and mobile phase composition control
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods
US20100252073A1 (en) * 2006-01-13 2010-10-07 Akzo Nobel Coatings International B.V Loop reactor for emulsion polymerisation
WO2013054180A1 (en) 2011-10-14 2013-04-18 Council Of Scientific & Industrial Research Continuous modular reactor
WO2014167506A1 (en) 2013-04-10 2014-10-16 Council Of Scientific & Industrial Research Flow reactor with pinched pipe sections for mixing and heat transfer
US11635054B1 (en) * 2022-08-04 2023-04-25 Wilfred S. Streeter Vertical water pumping system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112354507A (zh) * 2020-11-13 2021-02-12 山东新泽辉新材料科技有限公司 一种制备纳米氢氧化镁阻燃剂的反应装置

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US2299307A (en) * 1940-02-02 1942-10-20 Cornell Machine Company Method of and apparatus for treating materials
US2478051A (en) * 1944-03-24 1949-08-02 Carl H Nordell Hydraulic air compressor
US2755742A (en) * 1954-11-10 1956-07-24 Stanolind Oil & Gas Co Well pump
US3148037A (en) * 1957-08-09 1964-09-08 George C Szego Repeating chemical reactor apparatus
US3324093A (en) * 1963-10-21 1967-06-06 Phillips Petroleum Co Loop reactor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2299307A (en) * 1940-02-02 1942-10-20 Cornell Machine Company Method of and apparatus for treating materials
US2478051A (en) * 1944-03-24 1949-08-02 Carl H Nordell Hydraulic air compressor
US2755742A (en) * 1954-11-10 1956-07-24 Stanolind Oil & Gas Co Well pump
US3148037A (en) * 1957-08-09 1964-09-08 George C Szego Repeating chemical reactor apparatus
US3324093A (en) * 1963-10-21 1967-06-06 Phillips Petroleum Co Loop reactor

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595566A (en) * 1984-05-30 1986-06-17 Halliburton Company Continuous reactor design
AU626706B2 (en) * 1989-08-08 1992-08-06 Crown Berger Europe Limited Polymerisation processes and reactors
US5779994A (en) * 1995-10-16 1998-07-14 Bayer Aktiengesellschaft Tubular reactor
US6492184B1 (en) * 1998-04-03 2002-12-10 Symyx Technologies, Inc. Automated sampling methods with integral serial sample preparation for rapid characterization of polymers
US20030070988A1 (en) * 1998-04-03 2003-04-17 Miroslav Petro Rapid characterization of polymers
US6866786B2 (en) 1998-04-03 2005-03-15 Symyx Technologies, Inc. Rapid characterization of polymers
US6855258B2 (en) 1999-04-02 2005-02-15 Symyx Technologies, Inc. Methods for characterization of polymers using multi-dimensional liquid chromatography with parallel second-dimension sampling
US20030089663A1 (en) * 1999-04-02 2003-05-15 Miroslav Petro Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with parallel second-dimension sampling
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods
US6730228B2 (en) 2001-08-28 2004-05-04 Symyx Technologies, Inc. Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with regular second-dimension sampling
US20030080062A1 (en) * 2001-08-28 2003-05-01 Miroslav Petro Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with regular second-dimension sampling
US20060054543A1 (en) * 2004-09-03 2006-03-16 Symyx Technologies, Inc. System and method for rapid chromatography with fluid temperature and mobile phase composition control
US7507337B2 (en) 2004-09-03 2009-03-24 Symyx Technologies, Inc. System and method for rapid chromatography with fluid temperature and mobile phase composition control
US20100252073A1 (en) * 2006-01-13 2010-10-07 Akzo Nobel Coatings International B.V Loop reactor for emulsion polymerisation
US7956137B2 (en) * 2006-01-13 2011-06-07 Celanese International Corporation Loop reactor for emulsion polymerisation
WO2013054180A1 (en) 2011-10-14 2013-04-18 Council Of Scientific & Industrial Research Continuous modular reactor
WO2014167506A1 (en) 2013-04-10 2014-10-16 Council Of Scientific & Industrial Research Flow reactor with pinched pipe sections for mixing and heat transfer
US11635054B1 (en) * 2022-08-04 2023-04-25 Wilfred S. Streeter Vertical water pumping system

Also Published As

Publication number Publication date
GB1228831A (xx) 1971-04-21
DE1767354B2 (de) 1976-06-16
CH490113A (fr) 1970-05-15
ES353414A1 (es) 1969-10-01
DE1767354A1 (de) 1972-04-20
NL143822B (nl) 1974-11-15
DK137003B (da) 1978-01-02
SE339934B (xx) 1971-11-01
DK137003C (xx) 1978-06-05
IL29922A (en) 1973-03-30
AT289386B (de) 1971-04-26
IL29922A0 (en) 1969-03-27
NL6805942A (xx) 1968-11-04
BE714005A (xx) 1968-10-22
FR1547405A (fr) 1968-11-29
LU56003A1 (xx) 1969-02-05

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