EP1651654A1 - Method for making alkyhalosilanes - Google Patents
Method for making alkyhalosilanesInfo
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 38
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 26
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229940050176 methyl chloride Drugs 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 8
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 7
- 239000005048 methyldichlorosilane Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- -1 tin halides Chemical class 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000006011 Zinc phosphide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JTBAMRDUGCDKMS-UHFFFAOYSA-N dichloro-[dichloro(methyl)silyl]-methylsilane Chemical compound C[Si](Cl)(Cl)[Si](C)(Cl)Cl JTBAMRDUGCDKMS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940048462 zinc phosphide Drugs 0.000 description 1
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 Table
- 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
A method for making alkylhalosilanes is provided comprising reacting an alkyl halide and silicon in the presence of a copper catalyst comprising copper powder, particulate copper, copper flake, or combinations thereof and at least one co-catalyst.
Description
METHOD FOR MAKING ALKYHALOSILANES
BACKGROUND OF THE INVENTION
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.
Rochow, U.S. Pat. 2,380,995 discloses preparing a mixture of alkylhalosilanes by a direct reaction between powdered silicon and an alkyl halide in the presence of a copper-silicon alloy. This reaction is commonly referred to as the "direct method" or "direct process." The reaction can be summarized as follows:
(I)
Me2SiCl2
MeSiCl3
Si + eCl Me3SiCl
MeHSiCl2
Me2HSiCl
where Me is methyl.
In addition to the above methylchlorosilanes, "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.
Generally, it is desirable to yield high rates of production in the methylchlorosilane reaction as well as selectively produce dimethyldichlorosilane over the other products. New techniques are constantly being sought to improve the alkylhalosilane reaction.
SUMMARY OF THE INVENTION
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.
DESCRIPTION OF THE DRAWINGS
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.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, 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. Typically, the copper powder, particulated copper, copper flake, or combinations thereof has a surface area greater than 0.2 square meters per gram (m2/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" as used herein 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.
During the alkylhalosilane reaction, 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.
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. For instance, the phosphorus source can be copper phosphide, zinc phosphide, phosphorus trichloride, alkylphosphines such as triethylphosphine or trimethylphosphine or combinations thereof.
Although methyl chloride is preferably used in the alkylhalosilane of the present invention, other C(|. ) alkylchlorides, for example ethyl chloride, propyl chloride, etc., can be used. Correspondingly, the term "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.
Dimethyldichlorosilane has the highest commercial interest. A 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. Hence, the T/D product ratio is the object of numerous improvements to the alkylhalosilane reaction.
In addition to T/D ratio, another measure of performance of the methylchlorosilane reaction is the rate of crude methylchlorosilane formation. The reaction rate constant for methylchlorosilane formation is usually defined by those skilled in the art with the term "Kp". Kp 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. Thus, substantially high methyldichlorosilane is linked to poor methylchlorosilane performance. In the present invention, 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. In the present invention, substantially low residue is typically lower than about 3%.
Commonly, the alkylhalosilane reaction may be practiced in a fixed bed reactor. However, the alkylhalosilane reaction can be conducted in other types of reactors, such as fluid bed and stirred bed. More specifically, 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.
The expression "semi-continuous conditions" with respect to the description of the reaction of silicon and alkyl halide in the presence of a catalyst means that the reaction is conducted in a fluid bed reactor under semi-continuous conditions. With 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.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
Examples
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 meters2/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 lA 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.
• OMG and USB (U.S. Bronze) are manufacturers of copper sources. Figures 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.
While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the invention. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present invention.
Claims
1. 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.
2. The method in accordance with claim 1 , wherein the co-catalyst comprises zinc, tin, antimony, phosphorus, or combinations thereof.
3. The method in accordance with claim 1 , wherein the alkyl halide is methyl chloride.
4. The method in accordance with claim 1 , wherein said reaction is conducted in a fluid bed reactor.
5. The method in accordance with claim I , wherein said reaction is conducted in a fixed bed reactor.
6. The method in accordance with claim 1 , wherein said reaction is conducted in a stirred bed reactor.
7. The method in accordance with claim 1 , wherein the reaction is operated in batch mode.
8. The method in accordance with claim 1 , wherein the reaction is conducted at a temperature in a range between about 250°C and about 350°C.
9. The method in accordance with claim I , wherein the reaction is conducted at a temperature in a range between about 280°C and about 320°C.
10. The method in accordance with claim 1 , wherein the copper catalyst is present in a range between about 10% and about 60% by weight relative to the entire reactor bed.
1 1. The method in accordance with claim 10, wherein the copper catalyst is present in a range between about 15% and about 45% by weight relative to the entire reactor bed.
12. The method in accordance with claim 1 1 , wherein the copper catalyst is present in a range between about 20% and about 40% by weight relative to the entire reactor bed.
13. The method in accordance with claim I , wherein copper catalyst has a surface area greater than about 0.2 square meters per gram (m /g).
14. The method in accordance with claim 1 , wherein the silicon is powdered.
15. A method for making methylchlorosilanes comprising reacting a methyl chloride and powdered silicon in the presence of a copper catalyst comprising copper powder, particulated copper, copper flake, or combinations thereof and at least once co-catalyst comprising zinc, tin, antimony, phosphorus, or combinations thereof.
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US6258970B1 (en) * | 1999-04-19 | 2001-07-10 | General Electric Company | Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production |
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US6423860B1 (en) * | 2000-09-05 | 2002-07-23 | General Electric Company | Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production |
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