IL29922A - A method for carrying out polymerization or copolymerization reactions and apparatus therefor - Google Patents

Description

A method carrying out polymerization or copolymerlzation reactions and apparatus therefor to c reactions to novel and and facilitating chemical or of olefins or relates also to the polymers and in chemical ost frequently out in reactors continuously and reactor said to of the continuous or open Several reactors of this can be reactors being in in or in a of oeration differs from that customarily used in or quantities of essentially which do not contact of reacting in reactor the outside the course of use of the hal facilitate intermittent or episodic exchanges of the reactor reactions in and reactors carried out under transitional and the of the reactors vary Open operating continuously by since their operation is and bettor adapted thei possibilities are more limited than those of or hal typo inasmuch as the latter enable the operator to interfere at any time and to control the reaction as Conditions including and concentration can changed at new reagents can and all or part of the reaction products be drawn It is thus possible to take accoun reactional critical and kinetics of reactions and thus to an progression of the desired chemical capabilities of particular in case o In interference by chemist is possible in case of a single open reactor and barely possible in the case o of open Since cost of rapidly as the number of reactors used even this limited ability to exert closer control reactions open reactors io at a high She close control of one kind of reaction of industrial importance of It is polymerizations similar such as and ion of tho reaction is tantamount to the modification the product itself and to its gradual by following An o of invention to combine the simplicity and economy of continuous or reactors with flexibility and variability of the closed or Another of the invention is to facilitate the industrial of products which can be ured today only in the under conditions of reproducibility and regularity to obtain in the further the quantities invention is to facilitate the manufacture of especially polymers conforming to predetermined speci under conditions of automation equalling those tho classical continuous foregoing and other objects of invention arc in a representative in accordance invention fo out cal especially and particularly of olefins or by acting on separate quantities of reacting materials tained in cells nova le within fixed the cells being separated one another by movable hod is characterised in that the cells caused to sequentially past a plurality of stations where the transported measured quantities are continuously acted on by of operations such as o products off or recycling of modification of the operating condition taking of and oeasuresent of 1 Towards such a volume because of apart of times which operations carried out is function of the distance of the stations froia a point of accordance with invention the advantages of those of th Each cell is in effect the closed or She cells continuously a circuit travel one after each station of the conditions On the other in each conditions are transient or changing all reactors for continuous reactions in ttese conventional does not undertake a of the reaction act and discontinuous tities of the reacting the results obtained aro greatly it that there ho carried in tubular reactors reactions with measured tities of products separated by this suggestion provides only for obtaining piston discharge without organization o the evolution of the reaction within each interventions which take continuously in order to in nature or the qualities the product In accordance with method of invention materials aro preferably at least in prior to entering the tho roac ion t on out in tho In order to achieve it to introduce into reactor only preliminary or reagents until then aro iner In one of the it is possible to cyclically the conditions of in order to simultaneously different products intended or tho concentration of a catalyst or one or another reagent varied in accordance with a certain in order obtain in polymers different different average molecula Successive cells can be periodically specialised the production of a given polymer in different molecular in order to obtain by batch of a a molecular distribution with desired ef be obtained by a of fractions of reaction possibly with a of other fractions of the reaction so as to obtain of of the especially in anionic vary distribution of the molecular weights by at selected stations a catalyst or a j accordance tho and all their and many of their derivatives including their Of the various classical reaction methods such in in in and in Also conventional catalytic and methods can it is able to a liquid and reagents or monomers in gaseous condition be dissolved in a solvent OP liquo under It is to operate within a wide range of temperature and especially to have a temperature profile which is variable in the course of the reaction in each coil compartment of the profiles of pressure one end to the of reactor and thus the start to the end of the in accordance h invention can bo practiced by any suitable it is practiced by using a reactor She design of which part of the present reactor in accordance tho invention a tube of substantially shape and interior tho reaction sodium is caused to circulate in doses partitioned off by movable preferably of spherical tube forms a closed circuit a point of origin and a terminal which points separated by a tion which is impervious to the reaction medium and by a e or lock tho transfer of tho that tho separators are B tween the point of origin the terminal a permanent pressure differential by y suitable sufficient to keep the tube full and to assure the pulsion of the reaction medium and both substantially at in relation to the such speed preferably remaining invariable a any given point of tho circui In a tubo in is the difference in pressure two for the intake and is a function of the delivery rate and viscosity of the dance the inven the difference in pressure between the point of origin and terminal point should be such that the speed of the exceeds the value starting at the separators are carried along at the speed as tho s that effective tightness between the and tho wall of the tube is even if a considerable clearance Such minimum value depends on the viscosity of the the shape and the size of the tors and the inner wall the and the ascending or descending of the difference pressure to be established betwee the point of origin and the terminal point may be obtained by means of pumps which injec fluids the reaction medium at the point of origin and at intermediate points and by of discharge a place o can also hydrostatic Supplied by reservoirs placed at a higher level than t the discharge valve is regulated to the intake pressure the tubular reactor so as to maintain differential an and stabilise pressures rates of at all of the thereby facilitating the establishment of a at each renders th dwell o the medium in the subjects all parts of the reaction medium to the same evolutionary and thereby obtains a orm reaction the circuit by tube designed in such a as spread the load losses and the progressive drop of pressure over a great length in relation to the diameter of the so that on either of each separator and in the vicinity of it the pressures can bo considered practically Preferably the tubular reactor is of tubular elements ic are arranged almos zontally and separators have a which is to that of the reaction purpose of this provision is avoid subjecting the separators and the to different efects of A incline of the tube may the separators to move through the tube at a speed different from the speed of the reactio it is possible the tue in the vicinity of the points of origin and discharge so as quickly to to tors at the discharge end the speed of lation of the fluid into which they are introduced at the rectilinear elements of the tube can to ascend at a shallow whereby a pronounced descending inclination can be given curved elements connecting the rectilinear This tates the passage of separators through these curved a difference levels o substantial between near each other requires i general compensation in fozm of a reduction of the ance between the and the inner wall of the especially reaction medium a low is for in the vicinity of terminal poin where the tube preferably rises again to its if the final at end of the has not substantially In one of the the tubula reacto consists of a bundle of tubular elements which rectilinear and have the same lengt and are arranged almost horizontally and in parallel in superimosed layers at slightl different levels and are connected by cular Each tube is enclosed in a second cover which is and wherei a serving fo heating or coolin is The various injections or interventions preferably place in connectin separators a which them to roll in the of less friction for separators that roll than for those that this facilitates passage with minimum clearance through the semicircular Their density is close to the density the reaction medium so as to rende their low as possible and to eliminate zones of local contact or impact at the of the Towards such one may use of hollow spheres for by a welding or soldering together of hemispheres of of some suitable e separators ca consist of an material that chemically inert Of a form other than spherical may be provided hout exceeding the scope o the for a cylindrical shape which bulges out in the middle or is provided with sealing elements such the sealing ring of the of internal combustion The clearance between the separators and the inner wall of the tube difference between the radii of their cross sections is prefer but no for around one or two cent of the inne diameter of Absolute tightness is not relative tightness must increase as the Inclinatio the tube respect to the horizontal increases and as the spaed or the reaction Experience has shown that each bination o a given clearance between the separators and speed of the which the relative speed of the separators with respect the fluid substantially For horizontal tube lag liquid water afed spherical separators the of is of the inner of the the minimum is about 1 to 5 diameters ranging rom 10 to 500 In practice i is advisable to a substantially higher circulation in order to be above the critical speed avoid between separators and i case of In speeds ranging 10 the diamete of the per second if clearance the inner of the tube and separators is X to 2 hundredths of the diameter of the The distance between consecutive separators and the total number of separators present simultaneously can be varied within wide Although the invention comprises the e i which the reacto is divided into only two or a number of it is preferable to use a large number of compartments and of separators a reduction the length of each compartmen to less than 10 times the diameter of In good results are obtained th compartments the length of which ranges 10 to times the diameter of In of the invent the t terinal oint of the tubula and comprising a tight partition through which fluid cannot but which tho separators can transverse by of a or The interior volume the lock is tially the as that o a separator substantially no reaction is carried Various d be used to enable separators to clear the there two cylinders capable of sliding in a tight manner across the in one of its bases cavity corresponding to half the volume of a means of these two cylinders can seize a separator on one of the tight carry to tho and discnarse i or any other HE effect the movements of one or bot of the system consists application of at least one o the two cylinders with its hollow agains the tight wall which has an opening the dimensions of permi the passing of one this the two cylinders secure the closing and the opening for passing of Of It is possible use several gates in series or in to between the of a separator from tho circuit by means and its various for rinsing of the separator to eliminate any traces of the reacted product that may be its reactor accordance tte on affords great ease of of For by automatic in certain points of as temperature or it possible to upstream or increase or decrease of the for of the or also of the rate of understanding of additional o the invention may be gained fa a the detailed tion of several representative eqf and of the accompanying of the in Figure 1 is a plan view of a simplified of a reactor in accordance with the inventl is a perspective partly of pre of a reactor in accordance with the 3 a cross sectional view in of the view being the direction cated the Figure is a section o a portion of apparatus of figure is a longitudinal section of another portion apparatus of Figure Figure 6 is a detailed plan view of a portion the apparatus of 2 shown in Figure 7 is a sectional view in tte of th view being the direction indicated to arrows 10 to showing important characteristics of polymers respectively obtained in the case of 1 to 6 which 1 illustrates somewhat the and method in accordance with the invention as for to a and butadiene dissolved in of a catalyst of the butyl A tubula chamber 21 connected at a point of 22 and a terminal point to a distributor including lock The tubular contains reaction medium di vided into doses by of spherical separators or balls tube 21 surrounded by double covers each having an intake 28 and an 29 making i possible to circulate around the tube 21 a re lating the temperature o medium contained in t tube The division into sections of the double covers 27 makes it possible to maintain different ratures of the reaction medium at various points along its certain number of intervening stations is provided the route and the interventions take distributor is connected to an intake 51 under pressure which may for of solvent containing pressure i generated by a pump P in the intake the first intervening station 5 the catalyst is introduced by means At a second intervening station this mixing takes The reaction medium la drawn from the tube 21 through a 34 and orced through a tube 35 by means of a the same supplementary jection provided at a point by means of a pump 39 for a catalyst or one of At a third intervening part of medium drawn through a line by means of a pump 42 is At a fourth intervening station substance is drawn off by of a pump 44 the purpose of fo o the proportio of styrene the reaction can be slowed down or speeded up by reducing or increasing the temperature between of so that each of the 27 an additional means intervening in the the reaction medium through line 45 which is in communication with the point This line contains a variable discharge valve V lated b a sensor S which is connected to the valve and which senses the pressure of the reaction medium near several spherical separators 26 carried by the circulating reaction and the tion between separators when materials for added and decreases substance is drawn The diameter of balls 26 substantially the same as the diameter of adjacent to the distributor 24 comprises a traversed a bore in which slide two pistons 48 ani with the intake and point origin 22 on the hand and with the and the point 25 of the tubular chamber 21 on the The bore is closed off i the middle by a partition 50 with a hole 51 the diamete of is substantiall equal to the diameter of the separators of the pistons 48 and are formed with cavities 52 and which are substantially hemispherical and have a diameter substantially equal to the diamete of the separators The cavities 52 and 55 surrounded by shoulders and 55t adapted tightly to engage sides of the partition pistons 48 and are provided with ejectors 56 and respectivelyf biased by springs respectively for the purpose of ejection of the 26 as described Each of the pis ons 48 and is to slide in the Their movement is by hydraulic jacks Whenever the piston is against partition i prevents communication through the distributor 24 betwee the origin 22 and terminus 5 of tube the piston is sufficiently removed from the partition a separator carried along b the en enters the the plstai is about to be placed against the it seizes the se arator taking along practically no liquid in turn through the distributor 24 between the points 22 and piston can move now separator 26 isset free and carried along with the Seals 60 and 61 enable the pistons 48 and to tightly in the bore transfer of a separator om the termin point the point o origin 22 controlled or automatically by any suitable means including a automatic switch operated at timed intervals or by the passage of a through given point of the circui poin Figures to a preferred embodiment of accordance the reactor comprises a tube assembly by a of straigh or rectilinear segments tube 70 is by a double envelope 71 provided with an intake 72 and 75 for the heatin or cooling At each end is installed a fixed 74 and a movable flange successive straight tubes 70 are connected by a segmen or knee the latter being formed wo fixed flanges Θ1 which are bolted to the movable flanges In the flanges there are provided threaded bores 82 into which are screwed either stoppe o a connection to a line fo injection or drawing As figure the tubes 70 are not on level i each A upward slope is for in the direction of circulation hat the are correspondingly tates the passing o the balls 26 throug the knees this it sufficient to mount the tubes 70 o supports means of placed at the downstream end of each P 2 the point the terminal point distributor the main fluid intake and las tube is the one which considerable and requires inside machining great precision so that the clearance between the inner wall and the separators i order for the carried notwithstanding if the the reaction is sufficiently high a the end o the or if velocit through the tube is sufficiently great or the straight sections of the tube are sufficiently the separators move with the through the ascending even in the absence of precise figure 2 also feed o additional fluid as well as a point of intermediate injection figures 6 to illustrate a distributor comprising lock mean which has been operated with excellent results in combination with a tubular chamber such as the one shown in figures 2 to distributor comprises a block 120 with ous transverse and longitudinal bores and one transverse bores and serve for the passage of constituting the reaction the bore 122 with the reaction tube at the point of origin 22 and the 121 communicating the reaction at the terminal point role of the distributor to permit the of the balls from the bore 121 the through look means which prevents passage of bore 121 is connected to a forming the end of the tubular and to tube ting the for the luids and connected to the discharge The lowe bore 122 is connected to 124 forming the feed of the reactor and to tube 125 the o tubular distributor comprises furthermore two longitudinal bores and are superimposed and run into the bores 121 and at righ the bores slide pistons and There mounted i the 130 and at the of the bores 121 and 130 and a the of the bores and 1 1 137 which permit passage of fluids but prevent passage of balls 139 140 in 121 and Inlatable seals 141 held by rings and connected to intakes of fluids under pressure facilitate the of the pistons preventing of The two piston 133 and on the one hand and 134 and othe are connected flanges and by bolts end the flanges and themselves are to rods 154 of hydraulic jacks 1 piston 133 and have thei facing each and each of the a hemispherical cavity 57 with diameter which is substantial the of a separato whenever a separator 139 held between the a minimum of la the cavity together with the of pistons 133 and with an system comprising an spring and a screw 160 which is threaded into a cente thread The distributor has a vertical bore 170 connecting the bores 130 and 170 is to an take tube 171 for separator washing and to a tube fo of the washing 172 opens an intermediate socket 173 closed off by stopper which extends a center rod the vertical position of by means of a wheel shows a transverse 180 closed off by two glass 181 mounted in frames 183 184 screwed to block plates 181 and 182 possible to observe wha goes on the vertical tube assembly of the fixed elements constituting the including the block 1 0 and the jacks 155 and mounted on a fixed frame 162 consisting o angle which are assembled by any suitable means including welding and functioning of the distributor is easily figure 8 fluids kept the reactor arrive a the distributor and through it by means of the the bore 121 and the tube the separators are stopped by the screen transfer a separator pod by the screen in upper 121 to lower bore one operates hydraulic 155 and to cause the pistons and to approach each whereb the spherical separator is seized by one causes their displacement in a rator is to vertical bore separator released by 155 and 156 and drops into then driven by the circulating in the tubes 171 and The separator is stopped by the rod 175 by the pistons and displacing movemen then guides the separator the 122 whence it is carried by the fluid circulating in the tubes and has shown that tubular reactor such as the one described in 2 to 9 functions wit standing results and can be easily adapted to various polymerisations and For beat it is desirable that certain precautionary measures be taken during the start of it is not advisable to start the apparatus and the system of distribution of tho separators with a inert fo example a solvent or a solvent containing Regulating becomes much easier if the reaction is initiated whereafter the distribution of the separators can be In tho one obtains from the start a first matlon of what the viscosity of the reaction should he all along the In former with an viscosity be different the viscosity of the in process of and having the following numerical total the tubular liters inner diamete of the 24 length of individual 6 mm total the tubular 200 of the spherical average spacing between 1 rate of flow approximately liters pe a dwell of hours in the tubular reactor 2 intake 8 to 10 depending on the intake and dischare pressure to for liquid of 10 poises average cosity variable along chamber linear the Intake of reactor one under pressure of 10 40 of and of likewise introduced a from the intake some butyl at a rate of Pph pph is defined as 1 part by weight of substance added per 100 parte by weight of effected by means of pump the tube and forcing i into the tube throug a short pump has a delivery which is much higher tha that of the temperature is maintained at over the entire length the polymer obtained is dized stopped near the do end of the conversion obtained is close and the resulting ha an inherent viscosity of with a plasticity Of polymeric structure is as trans 50 The molecular distribution is shown in Figure graph For the purpose of h B shows the distribution of polymers obtained under conditions as nearly as possible the in the laborator in flasks of 250 and graphs and D show the molecular distributions of polymers obtained by continuous reactions vat using the sase catalytic system and substantially the same average reaction tines and As may the polymer obtained in accordance with the of the though prepared continuously is similar to prepared dlscontinuously the standard deviation of the molecular weights is eve slightly 2 proceeds as in in place of of one of a of time the butyl lithium added at a of one introduces pph of and and the orcing back at accelerated through a loop by of a pressure at intake is 8 and the is along the circuit resulting which is and is recovered at the In this conversion to inherent viscosity is and the plasticity of the polymeric structure as trans cis 1 Graph re shows the molecular distribution 1 1 of the polymer Graphs and C show the distributions of the polymers obtained a similar manner and of styrene i the ure i of Graph shows the molecula distribution obtained when the separators are eliminated from the and graph shows 3 preceding is except the lyst and are added in two Curing the one introduces pph butyl lithium and pph and maintains a temperature of In a second when conversion has attained substantially at a distance from point of of of the lengt the tubular one introduces of butyl lithium and pph in relation to the initial of monomer and reduces the ture to The polymer obtained has a dispersed molecular distribution shorn in graph in characteristics rate of inherent viscosity 2 plastic 60 The copolymer while having charac eristics simila to of example of rs advantage of being easier to One proceeds as in 2 and 5 hut using o The firs is at in the vicinity of the and consists of pph butyl lithium and pph The second injection is at conversi a a distance om the origin corresponding 20 of the length The third injection is a at a distance from the corresponding to of the length o the and consists pp butyl and calculated on the of the initial dwelling is two as in the other The pressure at 8 temperature is the firs and the second between the second and the third and between the third injection and the point of introduction of the antioxidant and the reaction The final polymer with a of conversio very close to has an viscosity of a plasticity of Its molecular distribution little wider than that of polymer in Example as show in the graph in figure Although the plasticity is the sane as in the inherent viscosity is One can thus at prepare polymers with the same plasticit but with higher inherent than the prepared by the conventional methods or polymers with inherent viscosity but greater a lower index of Example In this there is obtained a copolymer with a statistical distribution of the two in the using a polar compound such as tetrahydrofurane Or At the head the 40 hour of heptane of and of butadiene one lithium butyl a quantity of pp of the total of monomers The pressure a the star is Θ and the is maintained a all the par of copolymer is controlled in a whereby the percentage of styrene in the which is does not exceed one introduces a supplementary quantity of one successivel and of butadiene at points a distances and of the length of the reactor rom the point As a result of these additions of the average composition of the copolymer content structures is and the conversion of styrene monomer i polymerization may be continued furthe additions in stages of butadiene In such the content remains close to One may add butadiene at at a rate o as well as pph on of monome In such a one avoids the formation a styrene and the end i a statistical sequence of the two monomers of the latter 23 the styrene com ositions time appears in the graph in which shows the styrene percentage of tie polymer formed at successive points al ong the reaction tube as a function of the percentage conversion of the styrene 6 In this it is the aim to on the one the distribution of the monomers and in the on the especially the as in a French paten 5 of Societe introduces the under a pressure of 10 an hourly flow o liters of liters of and liters of One also adds pph butyl lithium and pph calculated on the total rate o monomer temperature at ong entire length of the tube a Inasmuch as the quantity is insufficient for obtaining complex with the the copolymer which not completely and becomes enriched in styrene hut has a low At point removed f om the origin a distance along the tube equal to o the length of the the butadiene complement is introduced at an hourly rate of the composition of the monomers is the position at successive points the tube of the lyro r which is formed becomes progressively riche in 29 At a point from origin a distance along the tube equal to of the length of one duces of calculated on the basis of the total The of the instantaneous compositions o copolymers of is indicated the graphs in figure 15 in the manne as The full line plots the instantaneous and the broken line the styrene content of the copolymer The obtained has the following inherent viscosityt plasticit trans contentj vitreous transition temperature during differential analysis graphs indicates as regards to molecular measured by means of the gel permeation chromatography as regards Examples 5 and the of styrene fixed in the copolymer by measurement of refraction index as a function of the rate conversion of the monomers there are provided in accordance with invention novel and methods and apparatus it possible to obtain wit much Greater ease than by conventional the close control of polymerizations and the polymers resulting therefro Many modifications spirit and scope o invention of the representative embodiments thereof disclosed above will readily occur to hose skilled in the invention is to be construed as extending to all the thereof within the scope of the insufficientOCRQuality

Claims (1)

1. 29922/2 Claims A method of carrying out polymerization or copolymerization reactions comprising the steps of continuously introducing solvent, monomer and catalyst material for reaction into a tubular reactor at a point of origin, said monomer being selected from the group consisting of olefins, diolefins, styrene, methyl methacrylate, and halogenated derivatives thereof, introducing at intervals &£ time at said point of origin spaced separators to divide said material into discrete batches, setting up a plurality of stations along the length of said tubular reactor, propelling said separators and batches through said tubular reactor and past said stations to a terminal point of said tubular reactor, changing the polymerization or copolymerization conditions at at least one of said stations in at least one of the following ways: (a) introducing more of the same kinds of solvent, monomer or catalyst material, (b) introducing other kinds of solvent, monomer or catalyst material, (c) extracting a portion of said material, and (d) changing the temperature of said material, each change in the volume of said batches being accompanied by a corresponding change in the spacing of said separators, the distance of said one station from said point of origin depending at least in part on&he time elapsed from the start of the reaction and on the flow speed of said material, whereby a polymer or copolymer is produced in said batches successively, discharging said polymer or copolymer from said tubular reactor at said terminal point, and recovering said solvent and separators for recycling with fresh solvent, monomer and catalyst material* 29922/2 A method according to Claim 1, comprising the step of modifying the change in said polymerization or copolymeriz-ation conditions with time to produce different products at said terminal point, further comprising the step of mixing said different products* A rhethod according to Claim 1, comprising the step of maintaining the velocity of said separators and batches substantially constant at each point long said tubular reactor betveen said point of origin; and said terminal point. A method according to Claim 1, comprising the step of maintaining the velocity of said separators and batches within the range of one to ten times the interior diameter of said tubular reactor per second at each point along said tubular reactor betveen said point of origin and said terminal point. A method according to claim 1, comprising the step of spacing said separators apart a distance equal to ten to two hundred times the interior diameter of said tubular reactor* A method of carrying out chemical reactions, substantially as hereinbefore described with reference to the Examples. A reaction product vhenever obtained by the method according to any of claims 1 to 6. Apparatus for carrying out chemical reactions by the method according to any of Claims 1 to 6 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 29922/2 and said 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 § 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 through said ube means at substantially the same velocity, whereby a continuous chemical reaction involving said materials occurs as said materials traverse said tube means* Apparatus according to Claim 8, wherein said velocity is constant at each point along said tube means* Apparatus according to Claim 8 wherein 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* Apparatus according to Claim .8 in which 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 11 in which , straight . segments define flow paths that run slightly uphill and said U-shaped segments define flow paths that run more steeply downhill* Apparatus according to Claim 11 comprising means connected to at least some of said U-shaped segments for selectively adding materials to and withdrawing materials from said cells* 29922/2 Apparatus according to Claim 8 in which said tube means has a circular interior cross section and said separator means comprises a plurality of spherical balls of a diameter substantially within the, range of .98 to .99 times the interior diameter of said tube, means and having a densit approximately the same as the density of said' materials* Apparatus according to Claim 8, in which the velocity of said materials and separator means is within the range of one to ten times the interior diameter of said tube means per second. Apparatus according to Claim 8, in which 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* Apparatus according to Claim 8 in which said lock comprises pistons formed with hemispherical cavities and said separator means comprises a plurality of spheres of the same diameter as said cavities, said pistons being slidable in a cylinder for enclosing said jspheres in said cavities while substantially excluding said materials and transferring said spheres from said terminal point to said point of origin* For the Applicants Dr. Yitzhak Hess