EP2049241A1 - Installation et procédé pour la fabrication industrielle continue de fluoroalkylchlorosilane - Google Patents

Installation et procédé pour la fabrication industrielle continue de fluoroalkylchlorosilane

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Publication number
EP2049241A1
EP2049241A1 EP07787213A EP07787213A EP2049241A1 EP 2049241 A1 EP2049241 A1 EP 2049241A1 EP 07787213 A EP07787213 A EP 07787213A EP 07787213 A EP07787213 A EP 07787213A EP 2049241 A1 EP2049241 A1 EP 2049241A1
Authority
EP
European Patent Office
Prior art keywords
reactor
reactors
reaction
catalyst
units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07787213A
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German (de)
English (en)
Inventor
Jürgen Erwin LANG
Georg Markowz
Dietmar Wewers
Harald Metz
Norbert Schladerbeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2049241A1 publication Critical patent/EP2049241A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00822—Metal
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00831—Glass
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00837—Materials of construction comprising coatings other than catalytically active coatings
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00869—Microreactors placed in parallel, on the same or on different supports
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00871—Modular assembly
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00873—Heat exchange
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing

Definitions

  • the present invention relates to a novel reactor and a plant for the continuous industrial production of fluoroalkylchlorosilanes by reacting an ⁇ , ß-unsaturated fluorine-substituted olefins with a HSi compound and a related method.
  • Organosilanes such as vinylchloro or vinylalkoxysilanes (EP 0 456 901 A1, EP 0 806 427 A2), chloroalkylchlorosilanes (DE-AS 28 15 316, EP 0 519 181 A1, DE 195 34 853 A1, EP 0 823 434 A1, EP 1 020 473 A2), alkylalkoxysilanes (EP 0 714 901 A1, DE 101 52 284 A1), fluoroalkylalkoxysilanes (EP 0 838 467 A1, DE 103 01 997 A1), aminoalkylalkoxysilanes (DE-OS 27 53 124, EP 0 709 391 A2 , EP 0 849 271 A2, EP 1 209 162 A2, EP 1 295 889 A2), glycidyloxyalkylalkoxysilanes (EP 1 070 721 A2, EP 0 934 947 A2), methacryloxy
  • Microstructured reactors as such for example for a continuous production of polyether alcohols (DE 10 2004 013 551 A1) or the synthesis of u. a. Ammonia, methanol, MTBE (WO 03/078052) are known. Also microreactors for catalytic reactions are known (WO 01/54807). However, so far the microreactor technology for the industrial production of organosilanes has been omitted or at least not realized. The tendency of alkoxy- and chlorosilanes to hydrolysis - even with small amounts of moisture - and corresponding caking in a Organosilanher einsstrom probably to be seen as a sustainable problem.
  • pre-reactors can be used in a particularly advantageous manner, which are equipped with packing, which even more targeted and effective separation of hydrolyzate or particles and thus a reduction in constipation tendency and downtime of the system can be achieved by deposits and caking in the reactor.
  • the educts vorzumischen immediately before the multi-element reactor continuously can also be done cold, then heat in the multi-element reactor and there targeted and continuously implement. It is also possible to add a catalyst to the educt mixture. Subsequently, the product can be worked up continuously, z. As in a evaporation, rectification and / or in a Kurzweg- or thin-film evaporator - to name just a few options.
  • the heat of reaction liberated during the reaction can be advantageously transferred via the large surface area of the interior walls of the reactor in relation to the reactor volume and, if provided, to a Heat transfer medium are dissipated.
  • a significant increase in the space-time yield of fast, heat-dissipating reactions is possible. This is made possible by a faster mixing of the educts, a higher average concentration level of the starting materials than in the batch process, ie no limitation by educt depletion, and / or an increase in temperature, which can usually cause an additional acceleration of the reaction.
  • the present invention enables the preservation of process reliability in a comparatively simple and economical manner.
  • a drastic process intensification in particular shortening of the process time under reaction conditions by more than 97% compared to the standard batch process can be achieved.
  • increased yields of up to 10% were achieved by higher conversions and selectivities.
  • the present reactions were carried out in a stainless steel multi-element reactor.
  • the implementation of said implementations can be dispensed with the use of special materials in an advantageous manner.
  • the reproducibility compared to comparable studies in batch processes could be significantly improved.
  • a multi-element reactor advantageously contains at least one interchangeable, preferably filled with preforms pre-reactor, a surprisingly long system life even without stoppages, which are caused by caking or deposits are made possible.
  • the multielement reactor before the start of the actual reaction with the reaction mixture, especially if this contains a homogeneous catalyst, to rinse, ie preconditioned.
  • the present invention thus provides a plant for the continuous industrial implementation of a reaction in which an ⁇ , ⁇ -unsaturated fluorine-substituted olefin A is reacted with an HSi compound B in the presence of a catalyst C and optionally further auxiliaries and the plant is at least mixed on the starting material ( 3) for the components A (1) and B (2), at least one multi-element reactor (5) which in turn contains at least two reactor units in the form of at least one replaceable prereactor (5.1) and at least one further reactor unit (5.3) connected downstream of the prereactor system, and based on a product work-up (8).
  • the present invention furthermore relates to a multielement reactor (5) for reacting hydrolyzable silanes, in particular those containing H-Si units, which in turn has at least two reactor units in the form of at least one replaceable prereactor (5.1) and at least one further reaction unit connected downstream of the prereactor system (5.3).
  • Prereactors (5.1) are preferred, which are equipped with packing.
  • Suitable fillers are for example - but not exclusively - structured packing, ie regular or irregular particles of the same or different size, preferably with an average particle size, the ⁇ 1/3, more preferably 1/5 to 1/100 of the free cross section of Cross-sectional area of the respective reactor unit (5.1) and the average particle cross-sectional area preferably 100 to 10 ⁇ 6 mm 2 corresponds, such as shavings, fibers / wool, spheres, splinters, strands with round or approximately circular or polygonal cross-section, spirals, cylinders, tubes, cups , Saddles, Honeycombs, Plates, Grids, fabrics, open-pored sponges, irregular shaped or hollow bodies, (structural) packings or containers of the aforementioned structural bodies, spherical bodies of metal, metal oxide, ceramic, glass or plastic, wherein said packing, for example - but not exclusively - made of steel , Stainless steel, titanium, copper, aluminum,
  • FIGS. 1 to 6 show flow diagrams of plants or plant parts as preferred embodiments of the present invention.
  • FIG. 1 shows a preferred continuous system in which the reactant components A and B are combined in unit (3), fed to unit (5), which may contain an immobilized catalyst, reacted therein and the reaction product in the unit (8) is worked up.
  • FIG. 2 shows a further preferred embodiment of an existing continuous plant in which a catalyst C, in particular a homogeneous catalyst, is fed to component B.
  • the catalyst can also be fed to the unit (3) or, as can be seen in FIG. 3, the catalyst C metered into a mixture of the components A and B shortly before entry into the multi-reactor unit (5).
  • a reactor unit is understood as meaning an element of the multielement reactor (5), each element representing an area or reaction space for the said reaction, cf. for example, (5.1) (reactor unit in the form of a pre-reactor) in Figure 4 and (5.5) [reactor unit of an integrated block reactor (5.3.1)] in FIG. 5 and (5.10) [reactor unit of a microtube bundle heat exchanger reactor (5.9)].
  • Reactor units of a multielement reactor (5) in the context of the present invention are in particular stainless steel or quartz glass capillaries, stainless steel tubes or well-dimensioned stainless steel reactors, for example pre-reactors (5.1), tubes (5.10) in microtube bundle heat exchanger reactors [e.g. B.
  • the inner walls of the reactor elements may be coated, for example with a ceramic layer, a layer of metal oxides, such as Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 , zeolites, silicates, to name only a few, but also organic polymers, in particular fluoropolymers, such as Teflon, are possible.
  • metal oxides such as Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 , zeolites, silicates, to name only a few, but also organic polymers, in particular fluoropolymers, such as Teflon, are possible.
  • a plant according to the invention comprises one or more multi-element reactors (5), which in turn are based on at least 2 to 1,000,000 reactor units, including all natural numbers in between, preferably from 3 to 10,000, in particular from 4 to 1,000 reactor units.
  • the reactor or reaction space of at least one reactor unit preferably has a semicircular, semi-oval, round, oval, triangular, square, rectangular or trapezoidal cross-section perpendicular to the flow direction.
  • a cross section preferably has a cross-sectional area of 75 ⁇ m 2 to 75 cm 2 .
  • Particularly preferred are cross-sectional areas of 0.7 to 120 mm 2 and all numerically intervening numerical values.
  • a diameter of> 30 ⁇ m to ⁇ 15 mm, in particular 150 ⁇ m to 10 mm is preferred.
  • Square cross-sectional areas preferably have edge lengths of> 30 ⁇ m to ⁇ 15 mm, preferably 0.1 to 12 mm.
  • reactor units with differently shaped cross-sectional areas can be present in a multielement reactor (5) of a system according to the invention.
  • the structure length in a reactor unit ie from entry of the reaction or product stream into the reactor unit, cf. z. B. (5.1 and 5.1.1) or (5.5 and 5.5.1), until the exit, cf. (5.1.2) or (5.5.2), preferably 5 cm to 500 m, including all numerically intervening numerical values, particularly preferably> 15 cm to 100 m, very particularly preferably 20 cm to 50 m, in particular 25 cm to 30 m.
  • reactor units whose respective reaction volume (also referred to as the reactor volume, that is to say the product of
  • Cross-sectional area and structure length 0.01 ml to 100 l, including all numerically intervening numerical values. This is particularly preferred
  • Reactor volume of a reactor unit of a plant according to the invention 0.05 ml to 10 1, very particularly preferably 1 ml to 5 1, very particularly preferably 3 ml to 2 l, in particular 5 ml to 500 ml.
  • systems according to the invention can be based on one or more multi-element reactors (5), which are preferably connected in parallel.
  • said multi-element reactors (5) can also be switched one behind the other so that the product which originates from the preceding multi-element reactor can be fed to the inlet of the subsequent multi-element reactor.
  • Present multielement reactors (5) can advantageously be combined with a reactant component stream (4) or (5.2), which is suitably divided into the respective sub-streams, cf. z. B. (5.4) in Figure 5 and (5.11) in Figure 6, are fed.
  • the product streams can be combined, cf. z. B. (5.7) in Figure 5, (5.12) in Figure 6 and (7), and then work up advantageously in a workup unit (8).
  • a processing unit (8) initially have a condensation stage or evaporation stage, which has a or several distillation stages.
  • a multielement reactor (5) of a plant according to the invention can be based on at least two stainless steel capillaries connected in parallel or on at least two quartz glass capillaries connected in parallel or at least one shell and tube heat exchanger reactor (5.9) or at least one integrated block reactor (5.3.1).
  • stainless steel capillaries, reactors or pre-reactors which advantageously consist of a high-strength, high-temperature-resistant and stainless steel; for example, but not exclusively, pre-reactors, capillaries, block reactors, shell-and-tube heat exchanger reactors, etc., are made of steel of the type 1.4571 or 1.4462, cf.
  • the steel facing the reaction chamber surface of a stainless steel capillary or a multi-element reactor with a polymer layer, for example a fluorine-containing layer, including Teflon, or a ceramic layer, preferably an optionally porous SiO 2 -, TiO 2 - or AI 2 O 3 layer, in particular for receiving a catalyst be equipped.
  • an integrated block reactor as can be seen, for example, as a temperature-controllable block reactor constructed from defined-structured metal plates (also referred to below as a plane) from http://www.heatric.com/phe-construction.html.
  • said structured metal plates or planes from which a block reactor can then be produced, can take place, for example, by etching, turning, cutting, milling, embossing, rolling, spark erosion, laser processing, plasma technology or another technique of the processing methods known per se.
  • structures such as grooves or joints, incorporated on one side of a metal plate, in particular a metal plate made of stainless steel.
  • the respective grooves or joints start on a front side of the metal plate, are continuous and usually end on the opposite end face of the metal plate.
  • FIG. 5 shows a plane of an integrated block reactor (5.3.1) with a plurality of reactor units or elements (5.5).
  • a level usually consists of a base plate made of metal with metal walls thereon (5.6), the reaction chambers (5.5) together with a cover plate made of metal and a unit for temperature control (6.5, 6.6), preferably a further level or textured metal plate, limit.
  • the unit (5.3.1) contains an area (5.4) for feeding and distributing the educt mixture (5.2) into the reactor elements (5.5) and a region (5.7) for combining the product streams from the reaction areas (5.5) and discharging the product stream ( 7).
  • an integrated block reactor (5.3.1)
  • several such previously described levels may be connected one above the other.
  • integrated block reactors (5.3.1) are advantageously surrounded by a temperature control unit (6.5, 6.6), which enables the heating or cooling of the block reactor (5.3.1), ie a targeted temperature control.
  • a medium (D) z. B.
  • Marlotherm or Mediatherm by means of a heat exchanger (6.7) tempered and fed via line (6.8) a pump (6.9) and line (6.1) of the temperature control unit (6.5) and via (6.6) and (6.2) removed and the heat exchanger unit (6.7 ).
  • a heat exchanger 6.7
  • a pump 6.9
  • an integrated block reactor (5.3.1) it is possible in an integrated block reactor (5.3.1) to optimally control the heat of reaction released by the shortest route, thereby allowing temperature peaks that result in a targeted reaction adversely affect, can avoid.
  • It is also possible to design the integrated block reactor (5.3.1) and the associated temperature control unit (6.5, 6.6) such that a temperature control plane is arranged between two reactor element planes, which guides the temperature control medium even more directionally between the areas (6.1, 6.5) and (6.6, 6.2).
  • a multielement reactor (5) comprising at least one pre-reactor (5.1) and at least one further reactor unit (5.3), for example a stainless steel capillary, or a pre-reactor (5.1) and at least one integrated block reactor (5.3.1) or a Pre-reactor (5.1) and at least one micro tube bundle heat exchanger reactor (5.9) includes, cf. FIG. 4.
  • the pre-reactor (5.1) is suitably tempered, that is H. cooled and / or heated, off (D, 6.3, 6.4).
  • a prereactor (5.1) in the context of the multi-element reactor (5) in particular for the implementation of silanes, is that in addition to carrying out the continuous reaction by a targeted separation and discharge of hydrolyzates or particles unplanned Stillg , Can advantageously minimize downtime.
  • the pre-reactors (5.1) equipped according to the invention can additionally be preceded and / or followed by filters for particle separation.
  • the multi-element reactor (5) at least two reactor units in the form of exchangeable pre-reactors (5.1), which are preferably equipped with packing, and at least one further, the pre-reactor downstream reactor unit (5.3) includes.
  • the educt components A and B can each be combined in a targeted manner from a storage unit by means of pumps and optionally by means of differential weighing system in the area (3).
  • components A and B are metered at ambient temperature, preferably at 10 to 40 ° C., and mixed in region (3). But you can also preheat at least one of the components, both components or feedstocks or the corresponding mixture.
  • the said storage unit can be conditioned and the storage containers can be designed to be temperature-controlled.
  • the multielement reactor (5) is preferably brought to or maintained at the desired operating temperature by means of a temperature control medium D (6.1, 6.2) so that undesirable temperature peaks and temperature fluctuations known from batch systems are advantageously avoided or adequately achieved in the present system according to the invention can become low.
  • the product or crude product stream (7) is continuously the product work-up (8), for example, a rectification, fed, for example, over head (10) a low-boiling product F, for example, used in excess and optimally recyclable silane, and on the Swamp (9) a heavy boiling product E can continuously decrease. It is also possible to remove side streams as a product from the unit (8).
  • the maximum particle diameter of the suspension catalyst should be less than 1/3, preferably 1/10 to 10 -2 , more preferably between 10 -4 and 10 -8 , the extent of the smallest free cross-sectional area of a reactor unit of the multi-element reactor (5).
  • FIG. 2 reveals that it is advantageous to meter in a said catalyst C to component B before it is combined with component A in region (3).
  • liquid auxiliaries for example but not exclusively, activators, initiators, stabilizers, inhibitors, solvents or diluents to the reactant components A and B, etc.
  • the catalyst C can be present, for example-but not exclusively-on the surface of the reaction space of the respective reactor elements.
  • a plant according to the invention for the continuous industrial implementation of the reaction of a said compound A with a compound B is optionally based in the presence of a catalyst and further auxiliaries on at least one Eduktzusammen entry (3), at least one multi-element reactor (5), which in turn contains at least two reactor units (5.1 and 5.3) according to the invention, and on a product work-up (8).
  • the reactants or feedstocks are provided in a storage unit for carrying out the reaction and fed or metered as required.
  • a system according to the invention is equipped with the measuring, metering, shut-off, transport, conveying, monitoring, control units and exhaust gas and waste disposal devices which are conventional in the art.
  • system according to the invention can be advantageously accommodated in a portable and stackable container and handled flexibly. So you can bring a system according to the invention quickly and flexibly, for example, to the respective educt or energy sources. With a system according to the invention, but also with all the advantages, it is possible to continuously provide product at the point at which the product is further processed or used further, for example directly at the customer's.
  • Another particularly noteworthy advantage of a plant according to the invention for continuous industrial implementation of a reaction of ⁇ , ß-unsaturated compounds A with a HSi compound B is that it now has a possibility, even small specialty products with sales volumes between 5 kg and 50,000 t pa, preferably 10 kg to 10 000 t pa, in a simple and economical manner to produce continuously and flexibly.
  • unnecessary downtime, the yield, the selectivity influencing temperature peaks and fluctuations and too long residence times and thus unwanted side reactions can be advantageously avoided.
  • such an installation can also be used optimally for the production of existing silanes from an economical, ecological and customer-friendly point of view.
  • a further subject matter of the present invention is a process for the continuous industrial production of a fluoroalkylchlorosilane of the general formula (I) F 3 C (CF 2 ) n (CH 2 ) 2 -Si (R ') m Cl 3 - m (I),
  • reaction of the starting material components A and B is carried out in the presence of a catalyst C and optionally further components in a multi-element reactor (5), which in turn on at least two reactor units in the form of at least one interchangeable prereactor (5.1) and at least one further, the pre-reactor downstream reactor unit (5.3).
  • the reaction is preferably carried out in at least one multielement reactor (5) whose reactor units consist of stainless steel or quartz glass or whose reaction spaces are delimited by stainless steel or quartz glass, wherein the surfaces of the reactor units can be coated or occupied, for example with Teflon.
  • reactor units whose respective cross-section is semicircular, semi-oval, round, oval, triangular, square, rectangular or trapezoidal.
  • reactor units are used whose respective cross-sectional area is 75 ⁇ m 2 to 75 cm 2 .
  • reactor units which have a structure length of 5 cm to 200 m, particularly preferably 10 cm to 120 m, very particularly preferably 15 cm to 80 m, in particular 18 cm to 30 m, including all possible numerical values Be included above areas.
  • reactor units are suitably used a whose respective reaction volume is 0.01 ml to 100 l including all numerically intervening numerical values, preferably 0.1 ml to 50 l, more preferably 1 ml to 20 l, most preferably 2 ml to 10 1, in particular 5 ml to 5 1.
  • the said reaction can also advantageously be carried out in a plant with a multielement reactor (5) which (i) has at least two parallel-connected pre-reactors (5.1) and at least one stainless steel capillary downstream of the pre-reactors, or (ii) at least two shunts Prereactors (5.1) and at least one downstream of the pre-reactors quartz glass capillaries or (iii) on at least two parallel connected pre-reactors (5.1) and at least one integrated block reactor (5.3.1) or (iv) on at least two parallel connected pre-reactors (5.1) and at least one Shell-and-tube heat exchanger reactor (5.9) based.
  • a multielement reactor (5) which (i) has at least two parallel-connected pre-reactors (5.1) and at least one stainless steel capillary downstream of the pre-reactors, or (ii) at least two shunts Prereactors (5.1) and at least one downstream of the pre-reactors quartz glass capillaries or (iii)
  • a multielement reactor (5) which contains at least two replaceable pre-reactors (5.1) according to the invention, these being equipped with fillers, as listed in particular above, for the separation of hydrolysis products of hydrolyzable silanes.
  • the process according to the invention is particularly preferably carried out in reactor units made of stainless steel.
  • the surface of the reactor units of the multielement reactor which is in contact with the starting material / product mixture is coated with a catalyst.
  • Multielementreaktor preconditioned by one or more rinses with a mixture of homogeneous catalyst C and component B or from homogeneous catalyst C and the components A and B or a short-term operation of the system, for example, for 10 to 120 minutes and optionally with a higher catalyst concentration.
  • the substances used for the preconditioning of the multielement reactor can be collected and later metered into the educt stream at least proportionally or fed directly to the product work-up and worked up.
  • reaction or product mixture can be present in one, two or three phases.
  • reaction is preferably carried out in a single-phase, in particular in the liquid phase.
  • the process of the invention is advantageously carried out using a multielement reactor at a temperature of 10 to 250 0 C at a pressure of 0.1 to 500 bar abs.
  • the reaction of components A and B, in particular a hydrosilylation, in the multielement reactor at a temperature of 50 to 200 ° C., preferably at 60 to 180 ° C., in particular at 100 to 120 ° C., and at a pressure of 0, is preferably carried out , 5 to 300 bar abs., Preferably at 1 to 200 bar abs., Particularly preferably at 2 to 50 bar abs., By.
  • the differential pressure in a system according to the invention ie between Eduktzusammen Replacement (3) and product processing (8), 1 to 10 bar abs.
  • a pressure-holding valve Preference is given to the pressure-holding valve from 1 to 100 bar abs., Preferably to 70 bar abs., Particularly preferably to 40 bar abs., In particular to a value between 10 to 35 bar abs., A.
  • the reaction can according to the invention at a linear velocity. (LV) of 1 to 1 ⁇ 10 4 h "1 i N. perform one.
  • the flow velocity of the material stream is situated in the reactor units preferably in the range of 0.0001 to 1 m / s i.
  • the ratio of reactor surface prevailing in accordance with the invention (A ) to the reactor volume (V) is preferable to have an AV ratio of 20 to 5,000 m 2 / m 3 - including all numerically possible individual values which are within the stated range - for advantageously carrying out the method according to the invention is a measure of the heat transfer and possible heterogeneous (wall) influences.
  • reaction in the process according to the invention is advantageously carried out at a mean residence time of from 10 seconds to 60 minutes, preferably from 1 to 30 minutes, more preferably from 2 to 20 minutes, in particular from 3 to 10 minutes.
  • mean residence time of from 10 seconds to 60 minutes, preferably from 1 to 30 minutes, more preferably from 2 to 20 minutes, in particular from 3 to 10 minutes.
  • Suitable components B in the process according to the invention are silanes of the general formula (II)
  • R ' is a C 1 to C 4 alkyl group, preferably methyl, m is 0 or 1 and X is a hydrolyzable group, preferably chloride, methoxy,
  • TCS trichlorosilane
  • TMOS trimethoxysilane
  • TEOS triethoxysilane
  • methyldimethoxysilane or methyldiethoxysilane are preferably used according to the invention.
  • the components A and B are preferably employed in the process according to the invention in a molar ratio A to B of 1: 5 to 100: 1, more preferably 1: 4 to 5: 1, very preferably 1: 2 to 2: 1, including all possible numbers within the previously mentioned areas.
  • a molar ratio of component B to component A of from 0.7 to 2 to 1 is preferred.
  • the process according to the invention is preferably carried out in the presence of a homogeneous catalyst C.
  • a "Speyer catalyst” cis- (Ph 3 P) 2 PtCl 2
  • complex catalysts of Pd, Rh, Ru, Cu, Ag, Au, Ir or those of other transition metals or noble metals where the known complex catalysts can be added in an organic, preferably polar solvent for example, but not limited to, ethers such as THF, ketones such as acetone, alcohols such as isopropanol, aliphatic or aromatic hydrocarbons such as toluene, xylene.
  • an activator for example in the form of an organic or inorganic acid such as HCl, H 2 SO 4 , H 3 PO 4 , mono- or dicarboxylic acids, HCOOH, H 3 C-COOH , Propionic Acid, Oxalic Acid, Succinic Acid, Citric Acid, Benzoic Acid, Phthalic Acid - just to name a few.
  • an organic or inorganic acid such as HCl, H 2 SO 4 , H 3 PO 4 , mono- or dicarboxylic acids, HCOOH, H 3 C-COOH , Propionic Acid, Oxalic Acid, Succinic Acid, Citric Acid, Benzoic Acid, Phthalic Acid - just to name a few.
  • an organic or inorganic acid to the reaction mixture can take on another advantageous function, for example as a stabilizer or inhibitor of impurities in the trace range.
  • the olefin component A is added to the catalyst, based on the metal, preferably in a molar ratio of 2,000,000: 1 to 1,000: 1, more preferably 1,000,000: 1 up to 4 000: 1, in particular from 500 000: 1 to 1 000: 1, and all possible numerical values within the abovementioned ranges.
  • an immobilized catalyst or heterogeneous catalyst from the series of transition metals or noble metals or a corresponding multielement catalyst for carrying out the hydrosilylation reaction. So you can, for example - but not exclusively - use precious metal sludge or precious metal on activated carbon. But you can also provide a fixed bed for receiving a heterogeneous catalyst in the field of multi-element reactor. So you can, for example - but not exclusively - also heterogeneous catalysts that bring on a carrier such as beads, strands, pellets, cylinders, stirrers, etc., inter alia SiO2, TiO2, Al2O3, ZrO2, in the reaction zone of the reactor units.
  • solvents or diluents such as alcohols, aliphatic and aromatic hydrocarbons, ethers, esters, ketones, CHCs, CFCs - to name but a few - can be used as auxiliaries.
  • Such adjuvants can be removed from the product, for example, in the product work-up.
  • inhibitors for example polymerization inhibitors or corresponding mixtures, can be used as additional auxiliaries in the present process.
  • the reactant components A, B and, if appropriate, C are metered in, and optionally further auxiliaries, and the mixture is mixed. It is endeavored to meter a homogeneous catalyst with an accuracy of ⁇ 20%, preferably ⁇ ⁇ 10%. In special cases, it is also possible to meter the homogeneous catalyst and optionally further auxiliaries into the mixture of components A and B only shortly before entry into the multielement reactor. Then you can the starting material mixture to the multi-element reactor and react the components under temperature control. However, it is also possible first to rinse or precondition the multielement reactor with a catalyst-containing educt or reactant mixture before the temperature is advanced to carry out the reaction.
  • the product streams (crude product) which are combined or obtained in the multielement reactor can subsequently be used in a product work-up of the plant according to the invention in a suitable manner, eg. B. by distillation with rectification work up. If appropriate, esterification of the product thus obtained with an alcohol or alcohol mixture can subsequently be carried out.
  • the process is preferably operated continuously.
  • inventive method using a system according to the invention advantageously continuously with a product output of 5 kg to 50 000 t p. a. and, for example, but not limited to, tridecafluoro-1-methyltetrahydro-octyltrichlorosilane.
  • 1, 2,2, tetrahydrooctyltrichlorosilane (Dynasylan ® 8061) used system consisted essentially of the reactant reservoir vessels, metering pumps (eg.
  • Diaphragm pumps control, measuring and dosing units, a T-mixer , two pre-reactors (diameter 5 mm, length 40 mm) equipped with fillers (stainless steel balls, diameter 1, 5 mm), a stainless steel capillary (1 mm diameter, 50 m length), a thermostatic bath with Temperature control for pre-reactors and capillaries, a pressure-holding valve, a stripping column operated continuously with N 2 and lines required in the system for feedstock guidance and for product, recycling and exhaust gas routing.
  • a T-mixer two pre-reactors (diameter 5 mm, length 40 mm) equipped with fillers (stainless steel balls, diameter 1, 5 mm), a stainless steel capillary (1 mm diameter, 50 m length), a thermostatic bath with Temperature control for pre-reactors and capillaries, a pressure-holding valve, a stripping column operated continuously with N 2 and lines required in the system for feedstock guidance and for product, recycling and exhaust gas routing.
  • the pressure was 25 ⁇ 10 bar.
  • the resulting top product essentially TCS, could be used as recycling stream.
  • Hydrosilylation product was continuously withdrawn from the bottom of the stripping column.
  • obtained fluoroalkyltrichlorosilane can be reacted with an alcohol to advantageously obtain fluoroalkylalkoxysilane.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne une installation, un réacteur et un procédé pour la réalisation industrielle continue d'une réaction selon laquelle une oléfine fluorosubstituée α,β-insaturée A est mise en réaction avec un composé HSi B en présence d'un catalyseur C et éventuellement d'adjuvants supplémentaires. L'installation selon l'invention comporte, au moins à la jonction des adduits (3) pour les composants A (1) et B (2), au moins un réacteur multiélément (5), comprenant lui-même au moins deux unités de réacteur sous forme de pré-réacteurs interchangeables (5.1) et au moins une unité de réacteur en aval des pré-réacteurs (5.3), et est fondée sur le traitement d'un produit (8).
EP07787213A 2006-08-10 2007-07-09 Installation et procédé pour la fabrication industrielle continue de fluoroalkylchlorosilane Withdrawn EP2049241A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006037402 2006-08-10
DE102007023759A DE102007023759A1 (de) 2006-08-10 2007-05-22 Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von Fluoralkylchlorsilan
PCT/EP2007/056931 WO2008017553A1 (fr) 2006-08-10 2007-07-09 Installation et procédé pour la fabrication industrielle continue de fluoroalkylchlorosilane

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EP2049241A1 true EP2049241A1 (fr) 2009-04-22

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US (1) US20090259063A1 (fr)
EP (1) EP2049241A1 (fr)
JP (1) JP2010500311A (fr)
KR (1) KR20090037460A (fr)
CN (1) CN101121721B (fr)
BR (1) BRPI0714847A2 (fr)
CA (1) CA2660404A1 (fr)
DE (1) DE102007023759A1 (fr)
NO (1) NO20091056L (fr)
RU (1) RU2009107980A (fr)
WO (1) WO2008017553A1 (fr)

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KR20090037460A (ko) 2009-04-15
RU2009107980A (ru) 2010-09-20
JP2010500311A (ja) 2010-01-07
WO2008017553A1 (fr) 2008-02-14
CA2660404A1 (fr) 2008-02-14
NO20091056L (no) 2009-03-20
CN101121721B (zh) 2013-04-10
US20090259063A1 (en) 2009-10-15
DE102007023759A1 (de) 2008-02-14
CN101121721A (zh) 2008-02-13

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