Classifications

• • 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
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
• • 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
  • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
  • C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00121—Controlling the temperature by direct heating or cooling
  • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00162—Controlling or regulating processes controlling the pressure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00164—Controlling or regulating processes controlling the flow
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00164—Controlling or regulating processes controlling the flow
  • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00245—Avoiding undesirable reactions or side-effects

Definitions

• the present invention relates to a process for the preparation of alkenylhalosilanes, in particular of vinyltrichlorosilane from vinyl chloride and trichlorosilane, and to a reactor which is particularly suitable for this purpose.
• Alkenylhalosilanes such as vinyltrichlorosilane (III), in particular the group consisting of
• Compound (III) vinyltrialkoxysilanes prepared via esterification reactions are important intermediate or intermediate technical products in organosilane chemistry. They are used, for example, as crosslinkers in plastics such as PVC, PP and PE.
• Trichlorosilane is typically carried out in a high-temperature reactor in the temperature range between 400 and 700 ° C and a pressure between 1 and 2 bar abs.
• the common methods are characterized in that either a tubular reactor or a reactor with a
• rotating displacer is used. Examples of this can be found in EP 0 438 666 A2, DE 199 18 1 14 A1 and DE 199 18 1 15 A1.
• the conversion of vinyl chloride can be adjusted only in the range of up to 80%, the selectivity to vinyltrichlorosilane is then at a maximum of about 86%. At conversions> 80%, the selectivity drops considerably due to the side reactions taking place.
• EP 0 438 666 A2 describes an annular gap reactor with a gap of 20 mm. The annular gap is formed via a rotating displacement body within the reactor shell.
• the documents DE 199 18 1 14 A1 and DE 199 18 1 15 A1 describe an annular gap reactor for the production of vinyltrichlorosilane, in which, after flowing through the annular gap, an adiabatic reaction zone is passed through and subsequently the
• the production output of the described reactor is 139 t vinyltrichlorosilane per month or specifically as space-time yield at 900 kg / (m 3 * h).
• Silicon tetrachloride 20.8 kg / h high boiler / more
• the production output of the described ring-gap reactor is 100 t of vinyltrichlorosilane per month or specifically as space-time yield 648 kg / (m 3 * h).
• the object of the present invention is to provide a process and a reactor suitable for the preparation of alkenyl halosilanes with increased yield and selectivity as compared to known processes and reactors and with a reduced tendency to side reactions.
• the present invention relates to a process for the preparation of alkenylhalogenosilanes by reacting alkenyl halide selected from the group of vinyl halide,
• Vinylidene halide or halide-halide allyl halide selected from the group consisting of mono- and di-o-trihalosilane in the gaseous phase in a reactor comprising a reaction tube (1) equipped with one inlet (2) at one end of the tube and one outlet (3) at the other end of the tube; a gas introduction device (4) which has a plurality of gas feed points (5) spaced apart from one another in the direction of the longitudinal axis of the reaction tube (1) and opening into the reaction tube (1), mono-, di- or trihalosilane passing through the inlet (2) in FIG the reaction tube (1) is passed and in the direction of the outlet (3) through the
• Reaction tube (1) flows, and wherein vinyl halide, vinylidene halide or allyl halide in sections through the gas feed points (5) in the gas stream in the interior of the
• Reaction tube (1) is initiated.
• halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably chlorine and bromine, in particular chlorine.
• the vinyl halides used according to the invention are vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide or mixtures of two or more thereof. Preference is given to using vinyl chloride and / or vinyl bromide, very particularly preferably vinyl chloride.
• the vinylidene halides used according to the invention are:
• Vinylidene chloride and / or vinylidene bromide is preferably used, very particularly preferably vinylidene chloride.
• allyl halides used according to the invention are allyl fluoride, allyl chloride, allyl bromide and allyl iodide or mixtures of two or more thereof.
• the monohalosilanes used according to the invention are:
• dihalosilanes are compounds of formula (Hal 1) (Hal 2) SiH 2, wherein Hall and Hal2 independently represent fluorine, chlorine, bromine or iodine.
• Examples of dihalosilanes are difluorosilane, dichlorosilane, dibromosilane, diiodosilane or mixed types such as chlorobromosilane, fluorochlorosilane or chloroiodosilane. They may also be mixtures of two or more of them. Preference is given to using dihalosilanes in which Hall and Hal 2 have the same meaning. Very particular preference is given to using dichlorosilane and / or dibromosilane, and in particular dichlorosilane.
• the trihalosilanes used according to the invention are compounds of the formula (Hal1) (Hal2) (Hal3) SiH, where Hall, Hal2 and Hal3, independently of one another, denote fluorine, chlorine, bromine or iodine.
• Examples of trihalosilanes are trifluorosilane, trichlorosilane, tribromosilane, triiodosilane or mixed types such as fluorochlorobromosilane, dichlorobromosilane or chlorodibromosilane. They may also be mixtures of two or more of them.
• Trihalosilanes are preferably used in which Hall, Hal2 and Hal3 have the same meaning. Very particular preference is given to using trichlorosilane and / or tribromosilane, and in particular trichlorosilane.
• the alkenyl halide is fed into the flowing mono-, di- or trihalosilane gas stream via several gas injection sites (5).
• the gas feed points (5) are arranged spaced apart in the direction of the longitudinal axis of the reaction tube (1) and allow the partial introduction of gas into the reaction tube (1).
• the gas feed points (5) preferably open centrally in the reaction tube (1), so that the introduced gas is introduced in sections at the location of the longitudinal axis of the reaction tube (1).
• one or more gas feed points (5) do not open centrally at the location of the longitudinal axis of the reaction tube (1).
• Alkenylhalogensilan can be increased particularly advantageous.
• the mono-, di- or trihalosilane can be fed completely into the reaction tube (1) at the inlet (2).
• a portion of the mono, di-iodo trihalosilane at the inlet (2) may be fed to the reaction tube (1) and the remaining portion is fed via one or more gas introduction devices (4) to the center of the reaction tube (1).
• the alkenyl halide is added in particular in the main flow direction.
• Alkenyl halide in the reaction tube (1) provided.
• the number of gas inlets (5) can vary over a wide range. Typically, two to ten
• Gas feed points (5) preferably three to six gas feed points (5) provided.
• the distance between two gas feed points (5) can also vary within wide limits. Typically, this distance is between 100 mm and 2000 mm.
• the gas feed points (5) are preferably arranged equidistantly; but it can also be chosen any other arrangement.
• the feeding of the alkenyl halide is usually carried out after the feed of the mono-, di-trihalosilane in the reactor.
• the distance between the first gas feed point (5) and the inlet (2) is between 20mm and 1000mm.
• Gas introduction device (4) provided means with which the flow rate of the
• Alkenylhalogenids at the gas feed points (5) can be varied.
• the flow rate of the alkenyl halide between the different gas feeds (5) is divided equally; Alternatively, the flow rate of the
• Alkenylhalogenids between the various gas feed (5) can be varied as desired.
• a quantity stream of alkenyl halide / (n-5) is preferably selected as the minimum amount per gas feed point (5), and the maximum amount per gas feed point (5) is selected as a quantity of alkenyl halide / (n-).
• n is the total number of
• n is greater than or equal to 2, preferably 3 to 15, more preferably 4 to 13, most preferably 5 to 12, especially 6, 7, 8, 9, 10 and 1 1.
• the use ratio of mono-, di- or trihalosilane to alkenyl halide the reaction can also be controlled.
• the ratio of mono-, di- or trihalosilane to alkenyl halide is between 1, 0 and 10 mol: mol, preferably between 2.0 and 4.0 mol: mol.
• reaction tube (1) At the end of the reaction tube (1), the reaction of mono-, di- or trihalosilane with alkenyl halide is largely completed.
• the product-containing reaction mixture can be discharged via the outlet (3) from the reaction tube (1) and supplied to further operations, for example, a separation of the product alkenylhalosilane from the
• the hot reaction mixture at the product end of the reaction tube (1) is quenched by quenching.
• This can preferably be done with liquid crude product, which preferably at the product end of the reaction tube (1) in the hot
• the reaction temperature can be selected within wide ranges.
• reaction pressure can also be selected within wide ranges.
• the pressure in the interior of the reaction tube (1) ( 0
• Reaction pressure between 1, 0 and 2.0 bar abs, more preferably between 1, 0 and 1, 5 bar abs.
• the course of the reaction can be controlled by the amount of added reactants. Preference is given to the partial flow of alkenyl halide to the
• the control can be done by temperature control circuits at the gas inlets (5).
• the residence time of the reaction mixture in the reactor can also be varied over wide ranges.
• the residence time of the reaction mixture in the reactor from the first gas feed point (5) to the outlet (3) is in the range between 0.5 and 10 seconds, preferably between 1.5 and 4 seconds.
• the present invention also relates to a tubular reactor which is suitable for carrying out gas-phase reactions and in particular for carrying out the above-described process for preparing alkenylhalosilane.
• a gas inlet device (4) having a plurality of, in the direction of the longitudinal axis of the reaction tube (1) spaced apart and in the reaction tube (1) opening gas feed points (5).
• Gas introduction device (4) are made, are resistant to high temperatures. These materials include, for example, iron-containing alloys, e.g. scale-resistant steels which contain chromium, nickel and / or titanium and / or molybdenum in addition to iron as an alloy constituent.
• iron-containing alloys e.g. scale-resistant steels which contain chromium, nickel and / or titanium and / or molybdenum in addition to iron as an alloy constituent.
• the reactor for the preparation of alkenylhalosilanes by reacting alkenyl halide with mono-, di- or trihalosilanes can be arranged both horizontally, vertically and obliquely. The nature of the attachment of the reactor has no effect on the
• the heating of the reactor i. the outer reaction tube (1) can be done in various ways.
• the most commonly used type is the direct electrical heating of the outer surface of the reaction tube (1).
• Another form of heating is to heat the outer tube via an intermediate medium, for example liquid lead.
• the heating of the outer tube by gas flames or by infrared radiation is possible.
• the nature of the reactor heating influences only insignificantly the sales achievable per reactor cross-sectional area.
• a line (10) is preferably provided, through which a part of the product (9) is returned to the vicinity of the outlet (3) and injected into the reaction mixture located there, whereby a shock-like cooling of the
• FIG. 1 describes the process according to the invention or the reactor according to the invention. Shown is the reaction tube (1), which is equipped on the left side with an inlet (2) for a reactant (7), for example for trichlorosilane. Following the inlet (2) is a preheating zone (6), in which the reactant (7) is heated to the required reaction temperature.
• a reactant (7) for example for trichlorosilane.
• a preheating zone (6) in which the reactant (7) is heated to the required reaction temperature.
• the reaction tube (1) open several gas feed points (5), which are fed by a gas inlet device (4). The mouth of these gas feed points (5) lies in each case in the middle of the pipe cross-section. By the gas feed points (5) is in sections another reactant (1 1),
• the reaction tube (1) ends on the right with an outlet (3) for the reaction mixture.
• This outlet (3) opens into a reservoir (8) for the cooled product (9).
• a portion of the product (9) is returned via line (10) under the action of the pump (12) in the vicinity of the outlet (3) and injected into the reaction mixture located there. This has a shocking cooling of the
• Reaction mixture and forming the cooled product (9) result. This is then passed through outlet (3) in the reservoir (8).
• Vinyl chloride was reacted with trichlorosilane in a tray reactor (diameter 200 mm, length 6000 mm) to vinyltrichlorosilane.
• the educt trichlorosilane was here in a
• Preheating section preheated to 400 ° C. At the top of the reactor was the feed of trichlorosilane. Vinyl chloride was also gaseous and preheated over several times
• the vinyl chloride Upon exiting the vinyl chloride at the feed points, the vinyl chloride was coated with trichlorosilane, and the reaction with vinyltrichlorosilane now took place in short reaction zones, avoiding the adverse wall reaction.
• the supplied trichlorosilane was supplied in excess and therefore could never be completely consumed at the vinyl chloride feed points.
• the reaction was carried out continuously in the described tray reactor with partial feed of vinyl chloride into the hot trichlorosilane stream.
• the reactor should in principle be regarded as a backmixing poor tubular reactor.
• the distribution of the vinyl chloride stream to several feed points enabled the
• Vinyl chloride were fed. 1000 mm behind the fourth and last feed point, the hot reaction gas was quenched with liquid crude product to about 40 ° C. The conversion of vinyl chloride was 86%, the selectivity was 95%.
• the reactor used has a diameter of 200mm and a length of 6000mm.
• the following mass flows of the reaction mixture were obtained at the outlet of the reactor:
• Silicon tetrachloride 17.4 kg / h high boiler / more
• this reactor had a monthly production capacity of 152 t vinyltrichlorosilane and a space-time yield of 1 .120 kg / (m 3 * h).
• a higher space-time yield was achieved than in the above-described comparative examples with reactors of the prior art and the vinyltrichlorosilane selectivity of the tray reactor used was also higher at 95% than in the comparative examples.
• the higher vinyltrichlorosilane selectivity was achieved by a smaller amount of by-product silicon tetrachloride and high boilers or other minor components.
• Advantages of the process according to the invention and of the reactor according to the invention of the type "tray reactor” are the increased selectivity and the increased space-time yield with respect to the target product vinyltrichlorosilane, because targeted wall reactions are prevented by the coating with a trichlorosilane stream , whereby in the considered reaction system fewer by-products, eg silicon tetrachloride, carbon black and 1, 2-bis (trichlorosilyl) ethane are formed.Also, the partial supply of vinyl chloride is an optimal
• the tray reactor used according to the invention can be operated at a significantly increased vinyl chloride conversion and vinyl chloride throughput because it works backmixing. This increases the space-time yield
• Vinyltrichlorosilane over the conventionally used reactors.
• the temperature profile can be optimized to maximize vinyltrichlorosilane selectivity.
• the vinyl chloride substream streams at the feed points are controlled via temperature control circuits.
• feed points for vinyl chloride provided with a 90 ° arc, so that the vinyl chloride is fed in the flow direction.

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• 2012
  • 2012-07-24 DE DE102012212915.4A patent/DE102012212915A1/de not_active Withdrawn
• 2013
  • 2013-05-28 JP JP2015523457A patent/JP6042540B2/ja not_active Expired - Fee Related
  • 2013-05-28 KR KR1020157003947A patent/KR101792923B1/ko not_active Expired - Fee Related
  • 2013-05-28 BR BR112015001368A patent/BR112015001368A2/pt not_active IP Right Cessation
  • 2013-05-28 EP EP13725367.0A patent/EP2877475B1/de not_active Not-in-force
  • 2013-05-28 WO PCT/EP2013/060910 patent/WO2014016014A1/de not_active Ceased
  • 2013-05-28 RU RU2015105915/04A patent/RU2605553C2/ru not_active IP Right Cessation
  • 2013-05-28 US US14/416,989 patent/US9272258B2/en not_active Expired - Fee Related

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