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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
  • B01J31/124—Silicones or siloxanes or comprising such units
  • B01J31/127—Silicones or siloxanes or comprising such units the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
• • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0254—Nitrogen containing compounds on mineral substrates
• • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/08—Compounds containing halogen
  • C01B33/107—Halogenated silanes
  • C01B33/10773—Halogenated silanes obtained by disproportionation and molecular rearrangement of halogenated silanes

Definitions

• the invention relates to a catalyst, its use as well as a process for the dismutation of hydrogen-containing halosilanes, in particular hydrogen-containing chlorosilanes.
• the dismutation reaction is used, for example, to prepare monosilane (SiH 4 ), monochlorosilane (CISiH 3 ) and also dichlorosilane (DCS, H 2 SiCl 2 ) from trichlorosilane (TCS, HSiCb) to form the coupling product silicon tetrachloride (STC, SiCl 4 ).
• the dismutation reaction to produce low chlorinated silanes such as monosilane, monochlorosilane or dichlorosilane, from higher chlorinated silanes, generally trichlorosilane, is performed to more rapidly adjust the chemical balance in the presence of catalysts.
• an exchange of hydrogen and chlorine atoms between two silane molecules is generally carried out according to the general reaction equation (1) in a so-called dismutation or disproportionation reaction.
• x can assume the values 1 to 3.
• the majority of the catalysts used are secondary and tertiary amines or quaternary ammonium salts (cf DE-AS 21 62 537). Thereby, to the
• reaction according to equation (1) is the preparation of dichlorosilane from trichlorosilane according to EP 0 285 937 A1.
• a process for the preparation of dichlorosilane by disproportionation of trichlorosilane is disclosed on a fixed catalyst bed in which gaseous dichlorosilane is removed and recovered under pressures between 0.8 and 1.2 bar and reactor temperatures between 10 0 C and the boiling point of the resulting reaction mixture; Portions of trichlorosilane are condensed and recycled to the reactor, the liquid reaction phase is partially withdrawn from the reactor and separated into tetrachlorosilane and trichlorosilane to be recycled to the reactor.
• catalysts for dismutation also usually ion exchangers are used, for.
• divinylbenzene crosslinked polystyrene resin having tertiary amine groups which is prepared by direct aminomethylation of a styrene-divinylbenzene copolymer (DE 100 57 521 A1), on solids which are attached to a scaffold made of polystyrene, crosslinked with divinylbenzene, amino or Alkylenamino groups, for example, dimethylamino groups (DE 100 61 680 A1, DE 100 17 168 A1), on anion-exchange resins based catalysts with tertiary amino groups or quaternary ammonium groups (DE 33 11 650 A1 ), amine-functionalized inorganic supports (DE 37 11 444) or according to DE 39 25 357 organopolysiloxane catalysts, such as N [(CH 2 ) 3Si ⁇ 3 / 2].
• the catalyst in the catalyst bed may correspond to a structured fabric packing or packing of tissue, alternatively, the catalyst bed may also contain packing or internals of catalytically active material.
• reaction and material separation offer the reactive rectification, because the dismutation reaction is a reaction limited by the chemical equilibrium in the conversion. This fact necessitates the separation of reaction products from the unreacted starting materials in order ultimately to complete the conversion in the overall process.
• the energetically ideal apparatus would be an infinitely high distillation column, in which on each tray or on each theoretical stage by a suitable catalyst or any length of time
• Apparatus would have the lowest possible energy consumption and thus the lowest possible operating costs [cf. Figure 6 and Sundmacher &
• Catalysts on inorganic supports for the production of dichlorosilane (DCS) from trichlorosilane by dismutation The listed catalysts (CH 3 CH 2 O) 3 Si (CH 2 ) 3 N (octyl) 2 and (CH 3 O) 3 Si (CH 2 ) SN (C 2 Hs) 2 have no high activity, so that the catalyst is used in relatively high amounts got to.
• the object of the present invention is to provide a catalyst system for dismutating hydrogen halosilanes which does not have the mentioned disadvantages and enables a more economical process for the preparation of higher hydrogenated hydrogen halosilanes.
• a catalyst according to the invention for the dismutation of hydrogen and halogen-containing silicon compounds comprising a support material and at least one linear, cyclic, branched and / or crosslinked aminoalkyl-functional siloxane and / or silanol, wherein at least one siloxane or silanol in an idealized form corresponds to general formula II,
• A is an aminoalkyl radical - (CH 2 ) 3 -N (R 1 ) 2
• R 1 is the same or different and iso-butyl, n-butyl, tert-butyl and / or a cyclohexyl group
• R 2 independently of one another hydrogen, a methyl, ethyl, n-propyl, iso-propyl
• the catalyst according to the invention has at least one siloxane or silanol with an aminoalkyl radical selected from 3- (N, N-di-n-butylamino), and a> 1 for a silanol ) propyl, 3- (N 1 N-di-tert-butylamino) propyl and / or 3- (N, N-di-iso-butylamino) propyl radical on.
• siloxane bonds (-O-Si-O-), for example, have been formed by condensation of at least two of the original groups -OR 2 , R 3 and / or R 4 .
• these catalysts allow a considerably faster adjustment of the equilibrium position in the dismutation reactions.
• a catalyst In order to produce and recover high purity or ultrahigh purity silicon compounds, a catalyst must be completely anhydrous and / or free of alcohols. High-purity silicon compounds are those whose degree of contamination in the ppb
• Ultrapure purity means impurities in the ppt range and below.
• Metal compounds should be at most in the ppb range up to the ppt range, preferably in the ppt range.
• the required purity can be determined by means of GC, IR, NMR,
• any porous or microporous material is suitable as the carrier material (Y), preferably silicon dioxide (SiO 2 ) or else zeolites, which are used may additionally contain aluminum, iron, titanium, potassium, sodium, calcium and / or magnesium.
• the silica may have an acidic, neutral or basic character.
• the carrier material is particulate and can be used, for example, in the form of shaped articles, such as spheres, pellets, rings, extruded rod-shaped bodies, trilopes, tubes, honeycomb, etc. or in the form of granules, granules or powders, spheres or pellets being preferred.
• the supported catalyst is preferably based on a microporous support having a pore volume of 100 to 1,000 mm 3 / g and a BET surface area of 10 to 500 nrvVg, preferably 50 to 400 nrvVg, particularly preferably 100 to 200 nrvVg.
• the expert can determine the pore volume and the BET surface area by means of methods known per se.
• the support material preferably has a geometric surface area of 100 to 2,000 m 2 / m 3 or a bulk volume of 0.1 to 2 kg / l, preferably of 0.2 to 1 kg / l, particularly preferably 0.4 to 0.9 kg / l, up.
• the ready-to-use, supported catalyst should be absolutely free of water, solvents, and oxygen, and should not release these materials on heating.
• the content of aminoalkylalkoxysilane compound used for modifying or impregnating the support material in the preparation of the catalyst is preferably from 0.1 to 40% by weight, based on the amount of support. Levels of from 1 to 25% by weight, more preferably from 10 to 20% by weight, based on the support material, are preferred.
• aminoalkyl-functional siloxane or silanol of the general formula (II) deposited on the carrier or condensed with the carrier material and advantageously covalently bound thereto via Y-O-Si
• the aminoalkyl-functional siloxane or silanol may also be deposited as an ammonium salt from a solvent, for example as a hydrohalide such as hydrochloride. In another alternative, it may also be deposited with a carboxylate or sulfate as the counterion.
• the invention furthermore relates to a process for the preparation of the catalysts according to the invention and to catalysts obtainable by the process in which a support material and at least one alkoxysilane of the general formula I
• A is an aminoalkyl radical - (CH 2 ) 3 -N (R 1 ) 2 and R 1 is identical or different and iso-butyl, n-butyl, tert-butyl and / or cyclohexyl group
• R 2 is hydrogen, methyl, ethyl, n-propyl or iso-propyl group
• R 3 and R 4 are independently a hydroxy, methoxy, ethoxy, n-propoxy, iso-propoxy , Methyl, ethyl, n-propyl and / or iso-propyl group
• aqueous alcohols for hydrolysis these are, for example, methanol, ethanol, isopropanol with a water content which is in particular in the range from 0.5 to 30% by weight, preferably from 0.5 to 10% by weight. %, more preferably between 1 to 5 wt .-%, is located.
• 0.5 to 50 mol of water in particular 1 to 20 mol of water, are advantageously used, ie added during the hydrolysis.
• all solvents are suitable in which the compound of formula I and / or the process product are soluble.
• Particular preference is given to hydrolyzing and / or condensing in aqueous ethanolic solution.
• the reaction may be carried out at temperatures between 0 and 150 0 C, under atmospheric pressure or reduced pressure, preferably at 1 to 1 000 mbar, more preferably at 50 to 800 mbar, in particular at 100 to 500 mbar, wherein the reaction is preferably in the boiling heat he follows.
• At least one alkoxysilane is selected from the group 3- (N, N-di-n-butylamino) propyltrimethoxysilane, 3- (N, N-di-n-butylamino) propyltriethoxysilane, 3- (N, N-di-) tert-butylamino) propylthmethoxysilan, 3- (N, N-di-tert-butylamino) - propyltriethoxysilane, 3- (N, N-di-iso-butylamino) propylthmethoxysilan or 3- (N 1 N-di- iso-butylamino ) Propyltriethoxysilane reacted in the presence of a carrier material, wherein the carrier material is preferably based on silica particles.
• alkoxysilanes of the general formula (I) may have the following substituents, where R 1 is an isobutyl, n-butyl or tert-butyl group, R 2 is a methyl, ethyl, n-propyl or isobutyl Propyl group and R 4 and R 3 of a methoxy, ethoxy, n-propoxy and / or iso-propoxy group correspond.
• the ready-to-use catalyst according to the invention for the production of highly pure or ultrahigh-purity silicon compounds must be absolutely anhydrous and / or free of alcohols.
• the coated catalyst support is advantageously dried to constant weight.
• the catalyst according to the invention is used in the dismutation of hydrogen and halogen-containing silicon compounds, in particular of 10
• Halosilanes such as trichlorosilane, which can react to dichlorosilane, monosilane, monochlorosilane and tetrachlorosilane.
• the invention also provides a process for the dismutation of hydrogen and halogen-containing silicon compounds on the aminoalkyl-functional catalyst according to the invention, which is located in a reactor, wherein the
• Halogen-containing silicon compound is brought into contact, wherein at least one siloxane or silanol in an idealized form of the general formula II,
• A is an aminoalkyl radical - (CH 2 ) 3 -N (R 1 ) 2
• R 1 is identical or different and iso-butyl, n-butyl, tert-butyl and / or cyclohexyl
• R 2 and R 4 independently of one another are hydroxyl, methoxy, ethoxy, n-propoxy, R 2 and R 4 are each independently of the other hydrogen, a methyl, ethyl, n-propyl, isopropyl group or Y; iso-propoxy, methyl, ethyl, n-propyl, iso-propyl and / or -OY, where Y is the support, HW is an acid, where W is an inorganic or organic acid radical, with a> 1 for the silanol, a> 2 for the siloxane and w> 0, and wherein at least a portion of the resulting reaction mixture is worked up.
• a preferred catalyst comprises siloxanes and / or silanols having at least one of the following aminoalkyl radicals A, 3- (N, N-di-n-butylamino) propyl, 3- (N, N-di-tert-butylamino) propyl -, and / or 3- (N, N-di-iso-butylamino) propyl groups, wherein the siloxanes and / or silanols in the presence of a carrier material, which is preferably based on the silica described above, were prepared. Depending on the reaction procedure and reactor, the most favorable form of carrier material can be selected. 1 1
• the catalyst is continuously flown in a reactor with at least one silicon compound of the general formula III H n Si m X (2m + 2-n) to be disiloxane, where X independently of one another corresponds to fluorine, chlorine, bromine and / or iodine and 1 ⁇ n ⁇ (2m + 2) and 1 ⁇ m ⁇ 12, preferably 1 ⁇ m ⁇ 6, more preferably trichlorosilane is converted to dichlorosilane, monochlorosilane and monosilane, which are subsequently separated.
• the silicon tetrachloride also formed is withdrawn from the chemical equilibrium discontinuously or continuously and can be purified separately.
• the catalyst is preferably in a catalyst bed.
• the separation of the halosilanes can take place by means of a column assigned to the reactor, which can be connected, for example, directly to the reactor.
• a column assigned to the reactor which can be connected, for example, directly to the reactor.
• higher hydrogenated silicon compounds can be recovered as low boilers at the top of the column and higher chlorinated silicon compounds are enriched as high boilers in a collecting vessel, while at least one unreacted silicon compound recovered as medium boilers on the column and again can be supplied to the associated reactor.
• the catalyst in a catalyst bed in a reactor is assigned to a separating tray of a column, for example a rectification column.
• This plant comprises an inventive
• Catalyst comprising a support material with siloxanes and / or silanols based on the reaction of an aminoalkylalkoxysilane of the general formula I, in particular siloxanes and / or silanols according to the general formula II, wherein the system comprises at least one distillation column (1) with a 12
• the starting or filling of the system with higher chlorinated silanes as reactant, in particular with trichlorosilane, and the Eduktzuschreib during operation of the system can be done for example via leads or taps of Eduktaufgabe (1.3) and / or on the column template (1.1).
• a removal of products can be carried out via the top of the column (1.8), the removal point (1.5) and / or the column template (1.4).
• the catalyst may be present in the catalyst bed (3) in the form of packing, which may be present, for example, as a bed or as a compressed mold body.
• the plant can be advantageously equipped with a heated column bottom (1.6, 1.1) and a cryogenic cooling (1.7) in the column head (1.2).
• the column (1) can be equipped with at least one column packing (8) and have at least one additional educt feed (1.3) or product removal (1.5). 13
• the catalyst bed of a side reactor is preferably operated at a temperature from -80 to 120 0 C, with the reactor or catalyst bed temperature regulated advantageously of a cooling or heating jacket of the reactor or controlled (2.1) will can.
• a sufficiently long residence time on the catalyst i. H. a sufficiently low catalyst loading is to ensure the approximate achievement of the chemical equilibrium
• the reactor as conventional reactors for comparable product flows.
• the usable reactors (2) should be dimensioned so that 80 to 98% of the equilibrium conversion can be achieved.
• the silicon compounds dichlorosilane, monochlorosilane and / or monosilane prepared by the process according to the invention are highly pure to ultra-high purity and are especially suitable as precursors for the production of silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide or silicon oxide and as precursors for generating epitaxial layers.
• the SiO 2 balls were predried for one hour at a pressure of 300 to 30 mbar and a bath temperature of 110 to 120 0 C and then dried for 9.5 hours at ⁇ 1 mbar.
• reaction mixture 150 m 2 / g, bulk density: 0.55 g / cm 3 ). The reaction mixture was
• the comparative examples clearly demonstrate that the catalyst of the invention is able to adjust the desired short residence times of trichlorosilane on the catalyst. Short residence times are particularly desirable in continuous process control.
• the catalyst prepared according to Example 3 was subjected to continuous operation over several months and checked its activity. In addition, the continuous operation was interrupted, the catalyst bed drained and put back into operation. The determination of the rates of dissolution showed a constant activity of the catalyst.

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• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
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• Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

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• 2007
  • 2007-12-06 DE DE102007059170A patent/DE102007059170A1/de not_active Withdrawn
• 2008
  • 2008-10-08 US US12/744,204 patent/US20100296994A1/en not_active Abandoned
  • 2008-10-08 UA UAA201008397A patent/UA104851C2/uk unknown
  • 2008-10-08 WO PCT/EP2008/063461 patent/WO2009071358A2/de active Application Filing
  • 2008-10-08 RU RU2010127424/04A patent/RU2492924C9/ru not_active IP Right Cessation
  • 2008-10-08 JP JP2010536387A patent/JP2011505246A/ja active Pending
  • 2008-10-08 EP EP13154517.0A patent/EP2591856A1/de not_active Withdrawn
  • 2008-10-08 BR BRPI0821154-0A patent/BRPI0821154A2/pt not_active IP Right Cessation
  • 2008-10-08 KR KR1020107012312A patent/KR20100092478A/ko not_active Application Discontinuation
  • 2008-10-08 EP EP08856913A patent/EP2222401A2/de not_active Withdrawn
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