EP1651654A1 - Procede de production d'alkylhalosilanes - Google Patents

Procede de production d'alkylhalosilanes

Info

Publication number
EP1651654A1
EP1651654A1 EP03819319A EP03819319A EP1651654A1 EP 1651654 A1 EP1651654 A1 EP 1651654A1 EP 03819319 A EP03819319 A EP 03819319A EP 03819319 A EP03819319 A EP 03819319A EP 1651654 A1 EP1651654 A1 EP 1651654A1
Authority
EP
European Patent Office
Prior art keywords
copper
accordance
catalyst
reaction
silicon
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Withdrawn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
EP03819319A
Other languages
German (de)
English (en)
Inventor
Larry Neil Lewis
Alan Carson Crawford
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.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP1651654A1 publication Critical patent/EP1651654A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis

Definitions

  • the present invention relates to a method for making alkylhalosilanes. More particularly, the present invention relates to a method for making alkylhalosilanes which includes silicon, alkyl halide and copper catalyst.
  • Residue is also formed during the production of methylchlorosilane crude.
  • Residue means products in the methylchlorosilane crude having a boiling point greater than about 70°C, at atmospheric pressure.
  • Residue consists of materials such as disilanes for example, symmetrical 1 ,1 , 2,2-tetrachlorodimethyldisilane; 1 ,1 ,2-trichlorotrimethydisilane; disiloxanes; disilymethylenes; and other higher boiling species for example, trisilanes; trisiloxanes; trisilmethylenes; etc.
  • disilanes for example, symmetrical 1 ,1 , 2,2-tetrachlorodimethyldisilane; 1 ,1 ,2-trichlorotrimethydisilane; disiloxanes; disilymethylenes; and other higher boiling species for example, trisilanes; trisiloxanes; trisilmethylene
  • the present invention provides a method for making alkylhalosilanes comprising reacting an alkyl halide and silicon in the presence of a copper catalyst comprising copper powder, particulated copper, copper flake, or combinations thereof and at least one co-catalyst.
  • Figure I shows the rate of crude methylchlorosilane formation from duplicate runs of the methylchlorosilane reaction using either copper flake catalyst or copper powder catalyst.
  • Figure 2 shows the ratio of methylchlorosilane to dimethyldichlorosilane (T/D) produced from duplicate runs of the methylchlorosilane reaction using either copper flake catalyst or copper powder catalyst.
  • Figure 3 shows weight percent of methyldichlorosilane produced from duplicate runs of the methylchlorosilane reaction using either copper flake catalyst or copper powder catalyst.
  • Figure 4 shows weight percent of residue produced from duplicate runs of the methylchlorosilane reaction using either copper flake catalyst or copper powder catalyst.
  • alkylhalosilanes are prepared by reacting silicon and an alkyl halide in the presence of a copper catalyst and at least one co-catalyst.
  • the copper catalyst is in the form of copper powder, particulated copper, copper flake, or combinations thereof. Copper powder, particulated copper, copper flake, or combinations thereof have been found to be suitable and cost effective catalyst for the formation of alkylhalosilanes.
  • the copper powder, particulated copper, copper flake, or combinations thereof has a surface area greater than 0.2 square meters per gram (m 2 /g).
  • the copper powder, particulated copper, copper flake, or combinations thereof is typically present in a range between about 1 % and about 6% by weight relative to the entire reactor bed, preferably in a range between about 1.5% by weight and about 4.5% by weight relative to the entire reactor bed, and more preferably in a range between about 2% and about 4% by weight relative to the entire reactor bed.
  • Optimum amounts of a given reactant can vary based on reaction conditions and the identity of other constituents can be readily determined by one skilled in the art.
  • Silicon used in the contact mass can have an iron (Fe) content in a range between about 0.1% and 1 % by weight based on total silicon, calcium (Ca) content in a range between about 0.01% and 0.2% by weight based on total silicon, and an aluminum (Al) content in a range between about 0.02% and 0.5% by weight based on total silicon.
  • the silicon typically has a particle size below about 700 microns, with an average size greater than about 20 microns and less than about 300 microns.
  • the mean diameter of the silicon particles is preferably in the range between about 100 microns and about 150 microns.
  • Silicon is usually obtained at a purity of at least about 98% by weight of silicon and it is then comminuted to particles of silicon in the above-described range for preparation of a contact mass.
  • Contact mass refers to a source of copper which is pre-heated with a silicon powder to form a contact mass.
  • the contact mass may be prepared by heating silicon and the copper catalyst in the presence of methyl chloride or other suitable gases at a temperature in a range between about 280°C and about 400°C in a furnace.
  • co-catalysts such as zinc, tin, antimony, and phosphorus may be used.
  • Zinc metal, halides of zinc, for example zinc chloride and zinc oxide have been found effective as components for the co-catalyst of the present invention.
  • Zinc (Zn) may be present in a range between about 0.01 weight % and about 1 weight % relative to the entire reactor bed.
  • Tin metal dust (-325 ASTM mesh), tin halides, such as tin tetrachloride, tin oxide, tetramethyl tin, and alkyl tin halide, and combinations thereof also can be used as a source of tin for making the co-catalyst component of the mass.
  • Tin (Sn) may be present in a range between about 10 parts per million and about 100 parts per million relative to the entire reactor bed.
  • phosphorus When phosphorus is a component of the alkylhalosilane reaction, it is typically present in a range between about 100 parts per million and about 1000 parts per million relative to the entire reactor bed. When phosphorus is added to the reactor bed, it can be supplied from a variety of sources.
  • the phosphorus source can be copper phosphide, zinc phosphide, phosphorus trichloride, alkylphosphines such as triethylphosphine or trimethylphosphine or combinations thereof.
  • alkylhalosilane includes dimethyldichlorosilane referred to as “D” or “Di”, which is the preferred methylchlorosilane referred to as “T” or “Tri”, and a variety of other silanes such as tetramethylsilane, trimethylchlorosilane, methyltrichlorosilane, silicon tetrachloride, trichlorosilane, methyldichlorosilane and dimethylchlorosilane.
  • T/D ratio is the weight ratio of methyltrichlorosilane to dimethyldichlorosilane in the crude methylchlorosilane reaction product.
  • An increase in the T/D ratio indicates that there is a decrease in the production of the preferred dimethyldichlorosilane.
  • the T/D product ratio is the object of numerous improvements to the alkylhalosilane reaction.
  • K p is the rate of methylchlorosilane production and is measured as grams of crude silane per grams of silicon per hour.
  • a substantially high rate is linked to enhanced methylchlorosilane formation.
  • a substantially high rate is typically greater than about 0.5 g silane/g Si-h.
  • the percent of methyldichlorosilane (MH) produced is also a measure of methylchlorosilane performance.
  • the hydride in methyldichlorosilane likely derives from the cracking of the methyl chloride, which is indicative of a poorly performing methylchlorosilane reaction.
  • substantially high methyldichlorosilane is linked to poor methylchlorosilane performance.
  • substantially high methyldichlorosilane is typically greater than about above 2%.
  • Residue formed is also a measure of the performance of the methylchlorosilane reaction.
  • a substantially low amount of residue is linked to enhanced methylchlorosilane formation.
  • substantially low residue is typically lower than about 3%.
  • the alkylhalosilane reaction may be practiced in a fixed bed reactor.
  • the alkylhalosilane reaction can be conducted in other types of reactors, such as fluid bed and stirred bed.
  • the fixed bed reactor is a column that contains silicon particles through which alkyl halide gas passes.
  • a stirred bed is similar to a fixed bed in which there is mechanical agitation of some sort in order to keep the bed in constant motion.
  • a fluidized bed reactor typically includes a bed of the contact mass, silicon particles, catalyst particles and promoter particles, which is fluidized; i.e., the silicon particles are suspended in the gas, typically methylchloride, as it passes through the reactor.
  • the alkylhalosilane reaction typically occurs under semi-continuous conditions or in batch mode at a temperature in a range between about 250°C and about 350°C, and preferably between about 280°C and about 320°C. It is also advisable to carry out the reaction under a pressure in a range between about 1 atmospheres and about 10 atmospheres in instances where a fluid bed reactor is used since higher pressure increases the rate of conversion of methyl chloride to methylchlorosilanes. Desirably, the pressure is in a range between about 1.1 atmospheres and about 3.5 atmospheres and preferably in a range between about 1.3 atmospheres and about 2.5 atmospheres.
  • reaction is conducted in a fluid bed reactor under semi-continuous conditions.
  • a semi-continuous reaction for example, the reactants are added and the reactor is run until about 50% of the silicon has been utilized. After about 50% silicon utilization, additional reactants of silicon and catalysts may be added.
  • a semi-continuous reaction is in contrast to a batch mode reaction. With a batch mode reaction, all of the reactant components are combined and reacted until most of the reactants are consumed. In order to proceed, the reaction has to be stopped and additional reactants added.
  • a fixed bed and stirred bed may both be run under batch conditions.
  • the fixed bed reactor was used to carry out the alkylhalosilane reaction.
  • the glass reactor was 100 mm long by 13 mm wide with a medium porosity glass frit located 80 mm from one end. Typically solid was loaded into the glass reactor and then heated under a flow of argon. The time zero of an experiment was when MeCl was turned on.
  • the product was collected at a -20°C condenser using a VWR model 1 156 recirculating chiller.
  • MeCl flow was controlled with a MKS model 1 179 mass flow controller using Kel F seals and a MKS type 247 four channel read out.
  • the furnace used was a A Nichrome"-wire-wound glass tube heated in two zones with two separate Antech Sales model 59690 Watlow temperature controllers.
  • Silicon Pulverized silicon with numerous trace elements was used. Particle size, size distribution, and trace element composition of the silicon are important in the Direct Process. To keep these variables under control, the same batch of silicon was used throughout this study. The silicon was produced by Elkem. A large quantity of this silicon was ground to surface area of 0.38 meters 2 /gm. The elemental composition of the silicon is listed in the Table. Major Components of Silicon Used in This Invention (ppm)
  • Running the fixed bed reactor A master batch of silicon powder and copper was prepared. Zinc was added to the master batch (30 mg), and 6 gms of master batch were loaded in the fixed bed reactor. The powder was lightly tapped so that the bed height was typically 4.7 to 4.9 cm. The reactor was installed in the system and argon flow was begun. The flow of argon was checked to be sure there were no system leaks. The bed was purged with argon for Vi hour at an argon flow rate of 40 cc/min (ca. 100 bed volumes). The heating system of the reactor was then turned on and typically within l A hour the bed temperature had stabilized at 310°C, the nominal operating temperature. Argon was turned off, and MeCl flow at 35 cc/min was begun.
  • Silane vapor leaving the reactor was recovered in a condenser operating at - 20°C. Liquid crude samples were periodically removed from the collector. The samples were weighed and later analyzed by gas chromatography using a HP 6890 gc equipped with an SPB210 capillary column (60 m x 530 uM x 3 uM film thickness).
  • the table below summarizes the powders evaluated.
  • the benchmark catalyst was the copper flake used commercially.
  • the OMG 831 had acceptable activity as a catalyst for the MCS reaction when compared to the Cu flake. Copper powder with high surface area and small particle size appears to be important for catalytic activity.
  • FIG. 1 -4 show the results of duplicate runs using either copper flake catalyst or copper OMG 831 powder catalyst in the MCS reaction.
  • the copper flake catalyst and the copper powder catalyst of the present invention are capable of yielding methylchlorosilane product, maintaining selectivity toward dimethyldichlorosilane, and maintaining a substantially low amount of methylchlorosilane residue that is formed.

Abstract

L'invention concerne un procédé de production d'alkylhalosilanes. Ce procédé consiste à faire réagir un halogénure d'alkyle et du silicium en présence d'un catalyseur à base de cuivre qui comprend de la poudre de cuivre, du cuivre particulaire, des paillettes de cuivre, ou des combinaisons de ces éléments et au moins un co-catalyseur.
EP03819319A 2003-07-31 2003-07-31 Procede de production d'alkylhalosilanes Withdrawn EP1651654A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2003/023920 WO2005082913A1 (fr) 2003-07-31 2003-07-31 Procédé de production d'alkylhalosilanes

Publications (1)

Publication Number Publication Date
EP1651654A1 true EP1651654A1 (fr) 2006-05-03

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EP03819319A Withdrawn EP1651654A1 (fr) 2003-07-31 2003-07-31 Procede de production d'alkylhalosilanes

Country Status (4)

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EP (1) EP1651654A1 (fr)
CN (1) CN1820014A (fr)
AU (1) AU2003257058A1 (fr)
WO (1) WO2005082913A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110107349A (ko) * 2008-12-23 2011-09-30 다우 코닝 코포레이션 오가노할로하이드로실란의 제조 공정
CN106000429B (zh) * 2016-06-15 2019-09-27 苏州铜宝锐新材料有限公司 一种催化剂及其应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4864044A (en) * 1985-02-15 1989-09-05 Union Carbide Corporation Tin containing activated silicon for the direct reaction
JP3743485B2 (ja) * 1999-04-13 2006-02-08 信越化学工業株式会社 オルガノハロシランの製造方法及び金属銅触媒の選定方法
US6258970B1 (en) * 1999-04-19 2001-07-10 General Electric Company Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production
EP1055675B1 (fr) * 1999-05-27 2003-05-21 General Electric Company Procédé pour la préparation d'alkylhalosilanes
JP3775467B2 (ja) * 1999-10-25 2006-05-17 信越化学工業株式会社 オルガノハロシランの製造方法
US6423860B1 (en) * 2000-09-05 2002-07-23 General Electric Company Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production
JP3812642B2 (ja) * 2001-02-14 2006-08-23 信越化学工業株式会社 オルガノハロシランの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005082913A1 *

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Publication number Publication date
WO2005082913A1 (fr) 2005-09-09
CN1820014A (zh) 2006-08-16
AU2003257058A1 (en) 2005-09-14

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