Process for producing chlorosilanes using a catalyst selected from the group of Co, Mo, W

Abstract

Generally unusable or difficultly useable dusts of ultrahigh purity silicon can be used to produce chlorosilanes under reasonable reaction conditions by employing a catalyst containing one or more of Co, Mo, W. The process may be incorporated into an integral plant for the production of polycrystalline silicon.

Claims

1. A process for producing chlorosilanes in a fluidized bed reactor comprising: reacting a hydrogen chloride-containing reaction gas with a particulate contact mass containing silicon and a catalyst, wherein the silicon consists of ultrahigh purity silicon having a purity>99.9%, wherein the catalyst comprises at least one element selected from the group consisting of Co, Mo and W, wherein the chlorosilanes have the general formula H.sub.nSiCl.sub.4-n and/or H.sub.mCL.sub.6-mSi.sub.2 where n=1-3 and m=0-4, and wherein the catalyst is present in the contact mass in a total amount of 100 to 400 ppmw, based on the weight of the contact mass, the catalyst content in ppmw calculated as the element.

2. The process of claim 1, wherein the catalyst further comprises at least one element selected from the group consisting of Zn, Cr and Ni.

3. The process of claim 1, wherein the catalyst is present in the contact mass in metallic, oxidic, carbidic, alloyed and/or salt form.

4. The process of claim 1, wherein the contact mass is a byproduct in the deposition of ultrahigh purity polycrystalline silicon and/or in the mechanical processing of ultrahigh purity polycrystalline/multicrystalline or single-crystal silicon.

5. The process of claim 4, wherein the catalyst is constituent of an abraded material from comminution equipment, plant parts and/or pipelines associated with the deposition or the mechanical processing of the ultrahigh purity silicon.

6. The process of claim 1, wherein the ultrahigh purity silicon has a Sauter mean diameter d.sub.32 of 0.5 to 150 μm.

7. The process of claim 1, wherein the ultrahigh purity silicon has a Sauter mean diameter d.sub.32 of 1 to 100 μm.

8. The process of claim 1, wherein the ultrahigh purity silicon has a Sauter mean diameter d.sub.32 of 5 to 80 μm.

9. The process of claim 1, wherein the process is performed at a temperature of 280° C. to 400° C.

10. The process of claim 1, wherein the process is performed at an absolute pressure in the fluidized bed reactor of 0 to 0.5 MPa.

11. The process of claim 1, wherein the hydrogen chloride and the ultrahigh purity silicon are present in a molar ratio of 10:1 to 3:1.

12. The process of claim 1, wherein the hydrogen chloride and the ultrahigh purity silicon are present in a molar ratio of 7:1 to 3:1.

13. The process of claim 1, wherein the reaction gas contains at least 50% by volume of hydrogen chloride.

14. The process of claim 1, wherein the reaction gas contains at least 70% by volume of hydrogen chloride.

15. The process of claim 1, wherein the ratio of fill height to reactor diameter is 10:1 to 1:1.

16. The process of claim 1, wherein at least one the chlorosilane is selected from the group consisting of monochlorosilane, dichlorosilane, trichlorosilane, Si.sub.2C.sub.6, and HSi.sub.2Cl.sub.5.

17. The process of claim 1, which is incorporated into an integrated system for producing polycrystalline silicon.

18. The process of claim 1, wherein one or more of Co, Mo, and W is/are present in the form of a carbide or chloride.

19. The process of claim 1, wherein the catalyst contains Mo and/or W.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 illustrates a fluidized bed reactor for performing the process of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(2) It has now been found that, surprisingly, even dusts composed of ultrahigh purity silicon (purity>99.9%) are even convertible into chlorosilanes, in particular TCS, in a fluidized bed reactor in the presence of small amounts of the elements cobalt, molybdenum, tungsten and mixtures thereof by hydrochlorination under typical reaction conditions (for example at a temperature of <380° C. and an absolute pressure between 0.2 and 0.5 MPa such as described in EP 1 586 537 A1, for example). A common conversion with mgSi is not necessary. In some cases, chlorosilane selectivity was increased further by additions of at least one of the elements zinc, chromium and nickel.

(3) The contact mass containing the ultrahigh purity silicon and the catalyst may be employed directly in existing fluidized bed reactors. Conversion to fixed bed reactors is not necessary. Chlorosilane selectivities and conversions of HCl comparable with the results obtained in the hydrochlorination of mgSi are moreover particularly advantageously achieved.

(4) The direct recovery of the ultrahigh purity silicon dusts generated as a byproduct provides a great economic advantage. In particular, so-called reprocessing costs such as melting or mixing the ultrahigh purity silicon dust with mgSi are avoided. Costs for disposal of the ultrahigh purity silicon dusts are likewise avoided. The procurement of mgSi can also be reduced.

(5) The catalyst is preferably present in the contact mass in a proportion of 1 to 900 ppmw, more preferably 10 to 700 ppmw, and most preferably 100 to 400 ppmw, based on the weight of the contact mass.

(6) The catalyst is preferably present in the contact mass in metallic, oxidic, carbidic, alloyed and/or salt-like form. Mixtures of the recited forms are also conceivable. It is particularly preferable when the catalyst is in the form of a carbide and/or chloride of the respective element. The catalyst may also be in the form of a silicide.

(7) The contact mass is preferably composed of particulate ultrahigh purity silicon (dust) and the catalyst. The composition of the ultrahigh purity silicon dust/of the contact mass may be determined by x-ray fluorescence analysis (XFA).

(8) In a preferred embodiment the contact mass is a byproduct generated in the deposition of polycrystalline silicon by the Siemens or granulate process. It may also be a byproduct generated in the mechanical processing of polycrystalline/multicrystalline or single-crystal silicon. The mechanical processing is in particular crushing and/or milling. If the contact mass is such a byproduct, purification prior to hydrochlorination is in principle not necessary. The ultrahigh purity silicon dust may be converted directly. Costly and complex purification steps are no longer required. Less preferred in principle is the use of silicon dusts generated as byproducts in sawing processes since these are generally severely contaminated as is described for example in DE 10 2014 007 354 A1.

(9) However, in some cases it may be preferable for the process according to the invention to be preceded by a purification of the contact mass.

(10) The catalyst may in particular be a constituent of an abraded material from comminution equipment such as hammers, roller mills, jaw crushers or chisels. It may further be a constituent of an abraded material of plant parts and/or pipelines. An abraded material in the case of plant parts may arise for example as a result of pneumatic conveying of the typically sharp-edged silicon dust. The catalyst may thus be present in the ultrahigh purity silicon dust in the form of foreign particles. It is customary for example for jaw crushers to be provided with hard metal coatings, for example tungsten carbide, for crushing ultrahigh purity silicon. Consequently the catalyst may already be present as tungsten carbide in the ultrahigh purity silicon dust generated as a byproduct. The addition of further amounts of catalyst may be avoided or at least minimized.

(11) In a further embodiment the ultrahigh purity silicon has a Sauter mean diameter d.sub.32 of 0.5 to 150 μm, preferably of 1 to 100 μm, more preferably of 5 to 80 μm, and in particular of 10 to 80 μm. The grain size is preferably 0.1 to 200 μm.

(12) The ultrahigh purity silicon dust generated as a byproduct may optionally be subjected to a milling process and/or classification process (for example sieving, sifting) to obtain the desired particle size.

(13) Determination of the grain size distribution/the Sauter mean diameter d.sub.32 may be effected according to ISO 13320 (laser diffraction) and/or ISO 13322 (image analysis). Calculation of average particle sizes/diameters from particle size distributions may be performed according to DIN ISO 9276-2.

(14) The process is preferably performed at a temperature of 280° C. to 400° C., more preferably 320° C. to 380° C., and most preferably 340° C. to 360° C. The temperature is the set temperature of the fluidized bed reactor. The set temperature is in principle specified as a target value by means of an adjustable temperature controller within a control loop and kept constant in the specified ranges by means of an appropriate cooling/heating system. Determination of the temperature may be effected for example by means of temperature sensors in the reactor interior (a plurality of temperature sensors and thus data points over the entire reactor height).

(15) The process is preferably performed at an absolute pressure in the fluidized bed reactor of 0 to 0.5 MPa, more preferably 0.02 to 0.4 MPa, and most preferably 0.05 to 0.25 MPa.

(16) During startup of the reactor, for example until formation of a stable fluidized bed, the values of pressure and temperature may differ from the values during the continuous reaction process. The same applies for the shutdown process.

(17) In a further embodiment hydrogen chloride (HCl) and ultrahigh purity silicon are present in the fluidized bed reactor in a molar ratio of 10:1 to 3:1, preferably 7:1 to 3:1, more preferably 5:1 to 3:1, and in particular 3.9:1 to 3.1:1. Particularly during the reaction, HCl and the contact mass are continuously added such that the abovementioned ratio is established. Preheating of the contact mass and/or of HCl is not required in principle but may be appropriate in some cases.

(18) It is preferable when the reaction gas contains at least 50% by volume, more preferably at least 70% by volume, and most preferably at least 90% by volume, of hydrogen chloride (HCl). In addition to HCl the reaction gas may further contain one or more components selected from the group comprising H.sub.2, H.sub.nSiCl.sub.4-n (n=0 to 4), HmCl.sub.6-mSi.sub.2 (m=0 to 6), H.sub.qCl.sub.6-qSi.sub.2O (q=0 to 4), CH.sub.4, C.sub.2H.sub.6, CO, CO.sub.2, O.sub.2, N.sub.2. These components may for example derive from HCl recovered in an integrated system. The reaction gas may further comprise a carrier gas, for example nitrogen or a noble gas such as argon. The reaction gas may further be admixed with hydrogen, in particular to influence the equilibrium position of the reaction. Hydrogen may also be present in recovered HCl as an impurity.

(19) Determination of the composition of the reaction gas is typically effected via Raman and infrared spectroscopy and gas chromatography before supply to the reactor. This may be effected not only via samples withdrawn individually followed by off-line analyses but also via online analytical instruments integrated into the system.

(20) It is preferable when the quotient of fill height to reactor diameter is 10:1 to 1:1, more preferably 8:1 to 2:1, and most preferably 6:1 to 3:1. The fill height essentially represents the center of mass of the fluidized bed and is dependent on the grain size distribution of the particles (fine particles tend to entail a large extent, and coarse particles a small extent, of the fluidized bed around the center of mass).

(21) Chlorosilanes produced with the process according to the invention are preferably at least one chlorosilane selected from the group comprising monochlorosilane, dichlorosilane, trichlorosilane, Si.sub.2Cl.sub.6 and HSi.sub.2Cl.sub.5. It is particularly preferable when TCS is produced.

(22) The process according to the invention is preferably incorporated in an integrated system for producing polycrystalline silicon. The integrated system in particular comprises the following processes: producing TCS by one of the processes according to the reactions (1), (2) and (3). Purifying the generated TCS to afford semiconductor-grade TCS. Depositing polycrystalline silicon, preferably by the Siemens process or as granulate. Further processing the generated polycrystalline silicon. Recycling the silicon dust generated in the production/further processing of the polycrystalline silicon by the process according to the invention.

(23) FIG. 1 shows a fluidized bed reactor 1 for performing the process according to the invention. The reaction gas 2 is preferably injected into the particulate contact mass from below and optionally from the side (for example tangentially or orthogonally to the gas stream from below), thus fluidizing the particles of the contact mass to form a fluidized bed 3. The volume flow may be determined by a flow meter (for example rotameter) in the reaction gas feed conduit to the reactor. To start the reaction the fluidized bed 3 is generally heated by means of a heating apparatus arranged externally to the reactor (not shown). Heating is typically not required during continuous operation. A portion of the particles is transported with the gas flow out of the fluidized bed 3 into the empty space 4 above the fluidized bed 3. The empty space 4 is characterized by a very low solids density, said density decreasing in the direction of the reactor outlet. The proportion of particles exiting the reactor with the gas flow is described as particle discharge 5.

EXAMPLES

(24) The examples were carried out in a fluidized bed reactor as described for example in U.S. Pat. No. 4092446.

(25) General Procedure:

(26) Nitrogen (carrier gas) was passed through the initially charged bed of contact mass until a fluidized layer was formed. The quotient of fluidized bed height to reactor diameter was set at a value of about 4. The reactor diameter was about 1 m. The fluidized bed was then heated to a temperature of 320° C. using an external heating apparatus. This temperature was kept constant over the entire experimental duration with the aid of a cooling means. Subsequently HCl was added and the contact mass replenished such that the height of the fluidized bed remained constant over the entire experimental duration and a constant molar ratio of the reactants (HCl:Si) of 3:1 was established. The pressure in the reactor was 0.1 MPa positive pressure over the entire experimental duration. After a running time of 48 h and 49 h both a liquid sample and a gas sample were withdrawn in each case. The condensable proportions of the product gas stream (chlorosilane gas stream) were condensed via a cold trap at −40° C. and analyzed by gas chromatography (GC) to determine TCS selectivity. Detection was via a thermal conductivity detector. The uncondensable proportion of the product gas stream was analyzed for unconverted HCl [% by volume] with an infrared spectrometer. The obtained values after 48 and 49 h were in each case used to form the average values. After each run the reactor was completely emptied and re-filled with contact mass.

Comparative Example 1

(27) As the contact mass exclusively ultrahigh purity silicon particles (purity>99.9%, maximum particle size 200 μm, d.sub.32=73 μm) were subjected to the above-described general procedure. Similarly to WO 2012/065892 A1, no formation of gaseous chlorosilanes was detected.

Comparative Example 2

(28) As the contact mass exclusively a silicon powder composed of commercially available mgSi (Fe content: 1.4% by weight, Al content: 0.2% by weight, Ca content: 0.015% by weight, maximum particle size 200 μm, d.sub.32=70 μm) was subjected to the above-described general procedure. As expected, conversion of the reactants to afford chlorosilanes took place. The amount of unconverted HCl was 7.5% by volume. TCS selectivity was 78%.

Working Example

(29) As the contact mass ultrahigh purity silicon dust (d.sub.32=68 μm) was subjected to the above-described general procedure, wherein the ultrahigh purity silicon dust contained as impurities as a consequence of manufacture (crushing of polycrystalline silicon) the following elements in the following proportions: Co: 10 ppmw, Mo: 5 ppmw, W: 72 ppmw, Zn: 154 ppmw, Ni: 35 ppmw, Cr: 79 ppmw. Surprisingly a conversion of the high-purity silicon to afford chlorosilanes took place under these conditions. The amount of unconverted HCl was 10.7% by volume. TCS selectivity was 81%.

(30) The results show that according to the inventive process ultrahigh purity silicon may be converted directly by hydrochlorination in a fluidized bed reactor. The results achieved (HCl conversion and TCS selectivity) are comparable with the results obtained when using mgSi. The process according to the invention even makes it possible to achieve higher TCS selectivities.