REACTOR AND METHOD FOR CONTINUOUS POLYMERIZATION

Abstract

The invention relates to a reactor and to a method for continuous polymerization, in which said reactor for the continuous production of polymers, particularly synthetic rubbers, contains at least one substantially tubular reactor housing (4), wherein said reactor housing (4) has a drive shaft (30) that is connected to at least one agitator (38) arranged such that it can rotate inside the reactor housing (4), and the agitator contains at least one, and preferably two, three or four helical mixing elements (24) which are designed to be preferably close to the wall or to come into contact with the wall.

Claims

1. A reactor for the continuous production of polymers, in particular synthetic rubbers, comprising at least one essentially tubular reactor housing, the reactor housing having a drive shaft which is rotatably arranged with at least one inside the reactor housing Stirrer is connected, the stirrer containing at least one, preferably two, three or four helical mixing elements, which are preferably designed close to the wall or in contact with the wall.

2. The reactor according to claim 1, characterized in that the geometric center axis is arranged essentially horizontally or essentially vertically.

3. The reactor according to claim 1, characterized in that it has an internal displacement body which is arranged essentially along the geometric central axis.

4. The reactor according to claim 1, characterized in that the stirrer has at least one helical mixing element designed close to the wall or in contact with the reactor housing, and at least one helical mixing element designed close to the wall or in contact with the wall of the internal displacement body.

5. The reactor according to claim 3, characterized in that the internal displacement body is designed in such a way that a temperature control medium can flow through it.

6. The reactor according to claim 1, characterized in that the helical mixing elements are designed such that the distance of the helical mixing elements to the reactor housing and the helical mixing elements to the internal displacement body 0 or more than 0 to 1% based on the radial diameter of the reactor housing.

7. The reactor according to one claim 1, characterized in that the reactor housing is connected to a conveying device for conveying starting materials into the reactor housing and/or for conveying products from the reactor housing.

8. The reactor according to claim 1, characterized in that it has a heat exchanger, the heat exchanger in turn having an outer jacket surrounding part of the reactor housing and preferably between the outer jacket and the Reactor housing a spiral partition is arranged to form a spiral heat exchanger channel.

9. The reactor according to claim 1, characterized in that it has a heat exchanger, the heat exchanger having a part of the outer casing surrounding part of the displacement body and preferably between the outer casing and the displacement body a spiral partition for forming a spiral heat exchanger channel is arranged.

10. The reactor according to claim 8, characterized in that the heat exchanger is suitable for temperature control with phase change, in particular boiling cooling.

11. The reactor according to claim 9, characterized in that the heat exchanger is suitable for temperature control with phase change, in particular boiling cooling.

12. The reactor according to claim 1, characterized in that the drive shaft is sealed via a double-acting mechanical seal arranged between the drive shaft and the reactor housing, the mechanical seal preferably containing a barrier medium which is inert under the polymerization conditions.

13. The reactor according to claim 1, characterized in that at least one preferably all helical mixing elements contain a groove into which a sealing tape is inserted.

14. The reactor according to claim 1, characterized in that the sealing tape is pressed via a spring mechanism onto the surfaces of the reactor housing or the internal displacement body, so that the sealing tape is close to the wall or in contact with the wall during operation of the reactor to the surfaces of the reactor housing or the internal displacement body.

15. The reactor according to claim 1, characterized in that the sealing tape made of polytetrafluoroethylene (PTFE), glass fiber reinforced PTFE, polyvinylidene fluoride (PVDF), ethylene-tetrafluorethylene copolymer (ETFE), polyether-ether eton (PEEK), Poiyoxymethylene (POM), polyethylene (PE) or a metallic alloy with non-eating properties compared to steel.

16. The reactor according to claim 1, characterized in that the helical mixing elements of the stirrer are made continuously over the entire reactor length from one part or from several parts which are connected to one another in a form-fitting manner, so that results in a continuous helix over the entire reactor length.

17. The reactor according to claim 1, characterized in that it contains more than one, preferably two, three or four helical mixing elements which are arranged at a uniform distance from one another in the direction of rotation.

18. The reactor according to claim 1, characterized in that the width of the helical mixing elements perpendicular to the surface of the reactor housing 10% to 100% of the annular gap width between the reactor housing and displacement body, preferably 15% to 50%, particularly preferably 20% to 40% and very particularly preferably 25% to 35%.

19. The reactor according to claim 1, characterized in that the placement of the helical mixing elements in relation to the surface of the reactor housing in the axial direction (slope) from =10 to <90; preferably from =30 to 60 and particularly preferably from =50 to 40.

20. The reactor according to claim 4, characterized in that the gradient of the helical mixing elements and the gradient of the helical mixing elements are different.

21. The reactor according to claim 1, characterized in that between the helical mixing elements and the helical mixing elements a support structure comprising, preferably consisting of 2 or more, preferably 4 to 8 support profiles running parallel to the geometric central axis is attached.

22. The reactor according to claim 21, characterized in that the support profiles have a rectangular cross-section and, compared to the radial direction, an adjustment of =0 to 90, preferably =30 to 60 and particularly preferably =40 to 50 exhibit.

23. The reactor according to claim 21, characterized in that the support profiles have a round cross-section and rectangular profiles are attached to these support profiles, which have an angle of =0 to 90, preferably =30 to 60 and particularly preferably have =40 to 50.

24. The reactor according to claim 1, characterized in that the speed of the drive shaft is selected such that the peripheral speed of the helical mixing elements on the surface of the reactor housing is between 0.05 m/s to 10 m/s, preferably 0.5 m/s to 6 m/s, particularly preferably 1 m/s to 5 m/s and very particularly preferably 1.5 m/s to 3 m/s.

25. The reactor according to claim 1, characterized in that the ratio of the reactor length L to reactor diameter D (L/D) is 1 to 15, particularly preferably 2 to 8 and very particularly preferably 3 to 6.

26. The reactor according to claim 1, characterized in that the ratio D/d of reactor housing diameter D and displacement body diameter d (D/d) 1.1 to 3.0, particularly preferably 1.2 to 2.0 and very particularly preferred 1.3 to 1.6.

27. (canceled)

28. (canceled)

29. A method for the continuous production of polymers by polymerization of polymerizable monomers, characterized in that the polymerization is carried out in a reactor according to claim 1.

30. The method according to claim 29, characterized in that in a reactor a circulating flow or loop flow of the starting materials and the products is impressed and during the polymerization the surfaces of the heat exchangers on the reactor housing and on the displacer body, any solids or gels that may have deposited are removed mechanically.

31. The method according to claim 30, characterized in that the mechanical removal is carried out by scraping or wiping.

Description

[0053] The invention is explained in more detail below with reference to the attached drawings on the basis of preferred exemplary embodiments.

[0054] It shows:

[0055] FIG. 1: a schematic side view of a reactor

[0056] FIG. 2: a schematic sectional view of the reactor with liquid cooling

[0057] FIG. 3: a schematic side view of the stirrer with two internal mixing elements

[0058] FIG. 4: a schematic sectional view of the displacement body for liquid cooling

[0059] FIG. 5: sectional view of the displacement body

[0060] FIG. 6: a schematic sectional view of a helical mixing element with a spring-mounted sealing tape

[0061] FIG. 7: a schematic detailed view of the spring band for the resilient mounting of the sealing band

[0062] FIG. 8: a schematic sectional view of the reactor for evaporative cooling. The reactor 1 shown in FIG. 1 has a geometric central axis 3 which is aligned parallel to a direction of gravity 2, that is to say vertically. The reactor 1 has a tubular reactor housing 4 which is closed on the end face by flanged end plates 5. Educts can be introduced into the tubular reactor housing 4 via at least one inlet 6. The resulting product can leave the reactor 1 via an outlet 7. Due to the stirring effect, there is an almost ideally mixed reaction solution inside the reactor. By continuously feeding the starting materials through the inlet 6, reaction solution is continuously displaced from the reactor housing 4 through outlet 7. The reactor 1 is thus operated continuously in order to carry out a continuous polymerization.

[0063] As shown in FIG. 2, the reaction heat generated during the polymerization can be removed via a heat exchanger 10 in the reactor housing 4 and via a heat exchanger 13 in the internal displacement body 14. The heat exchangers are limited on the side facing away from the reaction space by their outer surfaces (22 for heat exchangers 10, 23 for heat exchangers 13). In the case of heating or cooling without phase change in the cooling medium, the heat exchanger 10 in the reactor housing 4 and the heat exchanger 13 in the internal displacement body 14 are provided with spiral-shaped partition walls (16 for heat exchangers 10, 15 for heat exchangers 13 (FIG. 4)) which are provided in the Limit heat exchangers 10 and 13 spiral heat exchanger channels (18 for heat exchangers 10, 17 for heat exchangers 13 (FIG. 4), as a result of which a defined flow of the heat exchange medium from the inlet of the heat exchange medium (8 for heat exchanger 10 in the reactor housing, 11 for heat exchanger body 13 in the heat exchanger 13 Outlet of the heat exchange medium (9 for heat exchanger 10 in the reactor housing, 12 for heat exchanger 13 in the displacement body 14) is achieved. Sufficiently high flows of the heat exchange medium through the heat exchangers 10 and 13 generate a highly turbulent flow with high Reynolds numbers in the spiral heat exchanger channels 18 and 17, whereby a high heat transfer coefficient on the heat exchanger surfaces on the side of the heat exchange medium (20 for heat exchangers 10, 21 for heat exchangers 13) is achieved. Furthermore, in the case of cooling customary in exothermic polymerization reactions due to high cooling medium streams, the heating of the cooling media along the heat exchanger channels is limited, so that a uniform temperature control of the reaction space 19 is made possible. In principle, it is possible to arrange several heat exchangers in series, both in the reactor housing and in the displacement body, each of which has separate inlets and outlets, so that the heating of the cooling medium can be further reduced and the uniform temperature control of the reaction space is further improved.

[0064] In the reaction chamber 19, a stirrer is contained, in the exemplary embodiment consisting of 2 helical mixing elements 24 which are arranged close to the wall or in contact with the reactor housing 4 and 2 helical mixing elements 26 which are arranged near the wall or in contact with the outside of the displacement body 14. The number of inner and outer helices is determined by the cleaning frequency of the heat exchanger surfaces on the product side 32 and 33. With increasing reactor diameter and constant peripheral speed of the stirring elements on the reactor housing, the number of mixing elements increases in order to obtain an approximately constant cleaning frequency of 3-7 s.sup.1.

[0065] The helical mixing elements 24 and 26 are connected to the drive shaft 30 via a circular disk 28. At the end of the stirrer facing away from the drive shaft, the helical mixing elements 24 and 26 are connected to an annular disk 29 which has a tight play with the reactor housing 4 and/or the displacement body 14, and thus ensures additional centering of the stirrer. A support structure consisting of 2 or more support profiles 31 is used to stabilize the stirrer, which are firmly connected (welded) to the helices 24 and 26 at the contact points. Furthermore, the support profiles 31 are firmly connected (welded) to the circular disk 28 and the annular disk 29. The support profiles can consist of rods or tubes or of flat profiles.

[0066] The heat exchanger surfaces on the product side (32 for heat exchangers 10, 33 for heat exchanger 13) are cleaned by the mixing elements near or touching the wall, so that no insoluble polymer components (gel) adhere and the heat transfer coefficient on the product side is not impaired, Furthermore, the boundary layer on the heat exchanger surfaces is constantly renewed as a result, so that the heat flow from the interior of the reaction space to the heat exchanger surfaces is intensified.

[0067] In the exemplary embodiment, the outer helices 24 are oriented downwards in the direction of rotation, and the inner helices 26 are upwards. As a result, a loop flow is imposed on the product flow direction from the inlet 6 to the outlet 7, so that within the reaction space 19 there is an approximately ideal mixing and an approximately homogeneous temperature distribution, which leads to a narrow and defined molecular weight distribution in the polymerization reaction.

[0068] In production, it is very complex and costly to manufacture a helical mixing element with such accuracy that the required minimum wall distances or even wall contact are ensured at all points of the reactor. Therefore, the helical mixing element is manufactured with a larger wall distance and the wall near or wall contact is ensured via a spring-loaded sealing tape within a groove running over the entire helical mixing element.

[0069] FIG. 6 shows a cross section through a helical mixing element 24 and 26 with a sealing tape 36 which is resiliently mounted via a spring tape 35. The spring band 35 is inserted into the groove. The sealing tape is fitted into the groove of the helical mixing element with play. The sealing strips 36 of the outer helical mixing elements 24 are slightly above the insertion of the stirrer into the reaction space 19 on the reactor housing 4, the sealing strips 36 of the inner helical mixing elements 26 are slightly above the insertion of the stirrer into the reaction space 19 on the displacement body 14. When the stirrer is inserted, the sealing tapes are pressed into the groove against the spring force of the spring band, so that after the stirrer is inserted, they are pressed against the reactor housing or the displacer body by the spring band. In this way, a position of the sealing tapes in contact with the wall is achieved; in the event of manufacturing tolerances, the sealing tape is at least very close to the wall within the tolerances mentioned above, so that adequate wall cleaning and boundary layer renewal is ensured.

[0070] During operation, the groove can become clogged with insoluble polymer components (gel) or other solids, but the sealing tape remains in its position between the spring band and the reactor housing or between the spring band and displacement body with a sufficiently small wall clearance, only the function of the spring band is impaired. however, this is no longer required after the stirrer has been introduced in the company.

[0071] FIG. 7 shows an embodiment of the spring band 35. The spring force can be influenced and easily adjusted here by the type of material, the material thickness and the display of the spring arms.

[0072] FIG. 5 shows an embodiment of the displacement body 14 for a boiling cooling system with an evaporating cooling medium, such as e.g. Ethylene, propane or ammonia. Compared to the version for heat exchange media without phase change, the spiral partition in the heat exchanger of the displacement body is eliminated. In order to reduce the pressure losses in the cooling medium, a larger discharge nozzle for the 2-phase outlet mixture is recommended. 8 shows a schematic sectional view of a reactor with boiling cooling. It is advisable to arrange the drive shaft 30 at the lower end of the reactor and to arrange inlets 11 and outlets 12 for the heat exchange medium in the displacement body at the upper end of the reactor in order to ensure that the 2-phase cooling medium can escape from the coolant chamber.

A LIST OF REFERENCE NUMERALS IS GIVEN BELOW

[0073] 1. Reactor [0074] 2. Direction of Gravity [0075] 3. Geometric Central Axis [0076] 4. Tubular Reactor Housing [0077] 5. End Plates [0078] 6. Inlets [0079] 7. Outlets [0080] 8. Inlets heat exchange medium for heat exchangers in the reactor housing (10) [0081] 9. Outlets heat exchange medium for heat exchangers in the reactor housing (10) [0082] 10. Heat exchangers in the reactor housing [0083] 11. Inlets heat exchanger medium for heat exchanger in the displacement body (13) [0084] 12. Outlets heat exchange medium for heat exchangers in the displacement body (13) [0085] 13. Heat exchangers in the displacement body [0086] 14. Displacement bodies [0087] 15. Spiral partition for heat exchangers in the displacement body (13) [0088] 16. Spiral partition for heat exchanger in the reactor housing (10) [0089] 17. Spiral heat exchanger channel in the heat exchanger in the displacement body (13) [0090] 18. Spiral heat exchanger channel in the heat exchanger in the reactor housing (13) [0091] 19. Reaction space [0092] 20. Heat exchanger surface on the side of the heat exchange medium for heat exchanger in the reactor housing (10) [0093] 21. Heat exchanger surface on the side of the heat exchange medium for heat exchanger in the displacement body (13) [0094] 22. Outer jacket of the heat exchanger in the reactor housing (10) [0095] 23. Outer jacket of the heat exchanger in the displacement body (13) [0096] 24. Outer helical mixing element, close to the wall or in contact with the wall reactor housing 4 [0097] 25. Inner helical mixing element, close to the wall or touching the wall of the displacement body 14 [0098] 28. Circular disk [0099] 29. Washer [0100] 30. Drive shaft [0101] 31. Support profiles [0102] 32. Heat exchanger surface on the product page for heat exchangers in reactor housing (10) [0103] 33. Heat exchanger surface on the product page for heat exchangers in displacement body (13) [0104] 34. Direction of rotation [0105] 35. Spring band [0106] 36. Sealing tape [0107] 37. Groove [0108] 38. Stirring

EXAMPLE

[0109] In a test reactor with a reactor length L of 320 mm and a reactor diameter D 100 mm (L/D=3.2) with a central displacement body with a displacement body diameter d of 70 mm (d/D=0.7) and one Stirrer with 4 helical mixing elements over the entire reactor length, whereby 2 of the helical mixing elements close to the wall on the outer surface of the reactor housing and 2 of the helical mixing elements close to the wall on the surface of the internal displacement body (distance approx. 1 mm each), a starting solution was prepared 33.5% by weight solvent (alkane), monomers metered in continuously 1.5% by weight isoprene and 65% by weight isobutene. The starting material stream was dimensioned so that there was an average residence time of 15 minutes in the reactor. The reactor was completely filled with liquid.

[0110] To activate the polymerization reaction, a solution of the initiator (ethylaluminium dichloride, EADC) was additionally metered in in such an amount that the proportion of polymer in the total solution at the reactor outlet was between 10 and 15% by weight. The initiator was dissolved in the same solvent as the monomers.

[0111] The polymerization takes place under cryogenic conditions, i.e. the reactant solution and the solution containing the initiator were cooled to an inlet temperature of 80 to 60 C. before entering the reactor, and the reactor was also kept at a constant reaction temperature of 65 C. via a liquid cooling on the jacket side. A cooling of the internal displacement body was not necessary on this scale due to the high surface area to volume ratio of the housing wall to the reaction space.

[0112] The peripheral speed of the outer helical mixing elements was approximately 0.5 m/s.

[0113] Under the aforementioned conditions, butyl rubber (copolymer of isobutene and isoprene) was reproducibly obtained with a narrow molar mass distribution with a molar mass of 420-480 kg/mol and a polydispersity of 2.3 to 2.6.

[0114] The running times of the reactor were in the range of 5-10 days without a reduction in the heat transfer properties before removal of the insoluble polymer portion was necessary, in particular from the outgoing lines and parts of the stirrer, which led to an increase in pressure in the reactor and to a reduction in the reaction space ie lead to a reduction in the dwell time.