EP2771279A1

EP2771279A1 - Method for producing tetrahalosilanes

Info

Publication number: EP2771279A1
Application number: EP12780179.3A
Authority: EP
Inventors: Norbert Auner
Original assignee: Spawnt Private SARL
Current assignee: Spawnt Private SARL
Priority date: 2011-10-27
Filing date: 2012-10-26
Publication date: 2014-09-03
Also published as: WO2013060863A1; IN2014KN00895A; CN104169217A; KR20140103102A; JP2014530799A; US20140335006A1; DE102011117111A1

Abstract

A method for producing tetrahalosilanes (SiX₄) (X = halogen, especially Cl, F) from processed rock masses containing highly viscous hydrocarbons and SiO₂ and/or silicates or from the residual masses accumulating in the preparation is described. In the first variant of the method, the masses are heated in a flow of hydrogen halide, and the resultant (SiX₄) is collected and distilled. In the second variant, hydrogen fluoride (HF) and/or alkali or alkaline earth fluoride and sulfuric acid are added to the masses and the resulatnt (SiX₄) is collected and distilled. The method is characterized by an especially high efficiency, since the carbon that is present in the raw materials or residual masses is effectively used as a reducing agent or energy source.

Description

Process for the production of tetrahalosilanes

The present invention relates to a process for producing tetrahalosilanes (SiX ₄ ) (X = halogen, in particular Cl, F).

Tetrahalosilane is an important starting material for the production of silicon. In this regard, reference is made to the extensive state of the art.

The present invention has for its object to provide a process for the production of tetrahalosilanes, which is characterized by a particularly high efficiency.

This object is achieved by a process for the production of tetrahalosilanes (SiX ₄ ) (X = halogen, especially Cl, F) from recycled, highly viscous

Hydrocarbons and rock masses containing Si0 ₂ and / or silicates or in such a preparation

accumulating residue masses, in which the masses in

Halogenwasserstoffström be heated and the resulting SiX _{4 is} collected or distilled off.

According to the invention, use is made of the fact that in such prepared rock masses or

Residues still contain carbon in the form of high-viscosity hydrocarbons. This carbon is used to reduce the present in the rock masses Si0 ₂

and / or the corresponding silicates used, so that in this way on an already existing in the starting material

Reducing agent used and this is used specifically for the production of tetrahalosilanes, which can then be converted in further reaction steps to the desired Si. It is essential that the starting materials in question (rock masses, residue masses) contain enough carbon to provide the desired

Reduction of Si0 ₂ or silicates can be performed. The masses contain, for example, highly viscous Hydrocarbons in the form of bitumen or tar. In order to determine whether a sufficient amount of carbon is present, the C content of the masses is preferably determined. If this is insufficient, carbon is added to the masses before or during heating. In this case, preferably cheaper carbon (hard coal, dried biomass, coal, etc.) is used.

In a special variant of the process according to the invention, the masses for residual water removal are heated to about 400-500 ° C. and then to about 1000-1300 ° C. for obtaining S1X ₄ .

Such rock masses are, for example, oil sands or oil shale. The term used

"Rock mass" should also cover oil sludge, although this is not a rock. For example, these rock masses become low-viscosity

Hydrocarbons (petroleum) obtained, via today's conventional method, according to which the residues, preferably

Si0 ₂ ~ containing material and highly viscous hydrocarbon radicals (bitumen residues), as starting materials for the

inventive method can be used. In particular, the determination of the C content, if appropriate the addition of carbon and the heating in two stages (400-500 ° C. for residual water removal, 1000 ×

1300 "C for reduction.) The heating to 1000-1300 ° C takes place in the hydrogen halide stream, with S1X ₄ in a cold trap

is collected or distilled off. The energy supply

can be conventional or alternatively by

Electromagnetic alternating fields (for example, microwave) done.

In another embodiment of the invention

The method is achieved by a process for the production of tetrahalosilanes (SiX)

(X = halogen, especially Cl, F) from recycled,

highly viscous hydrocarbons and S1O ₂ and / or silicates containing rock masses or those in such

Treatment solved residue residues, in which the Bulk with hydrofluoric acid (HF) and / or alkali or

Erdalkalifluorid and are mixed with sulfuric acid and the resulting SiX _{4 is} collected or distilled off. In this process, the implementation of the

Starting substances with hydrofluoric acid or corresponding

Fluorides. Here, the in the starting substances

existing carbon is used as a suitable energy source for the further processing of the SiX obtained to Si, so that also in this process variant, an effective or efficient use of existing materials in the starting materials. SiF _{4 is} obtained in situ in this process. As already mentioned, the further processing of the

SiX _{4 obtained} to Si in a known manner.

For example, SiX ₄ can be converted plasma-chemically into polyhalosilanes. Thermolysis at about 800-1000 ° C then gives Si and SiX ₄ which can then be recycled.

The residue contains alkali-alkaline earth oxides and / or

Halides easily separable from SiX. The used for the process according to the invention

prepared rock masses or residue masses are preferably contained by removal of the rock contained in the rock

Petroleum, in particular via conventional mining and

Extraction method, such as SAGD (steam assisted gravity

drainage), CSS (cyclic steam stimulation), THAI (toe-to-heel air injection), VAPEX (vapor extraction process).

It is assumed that for the inventive

Process prepared rock mass or residue masses are used, from which by appropriate

Preparation or recovery process already valuable low-viscosity hydrocarbons (petroleum) have been removed. In the rock masses or residues therefore remain only higher-viscosity hydrocarbons, which are for the According to the invention carried out reduction process or as an energy source for the further processing of S1X ₄ to Si. However, the invention does not exclude that for the process according to the invention also masses are used, of which previously no low-viscosity

Hydrocarbons have been removed. This may be, for example, rock masses which have a relatively low proportion of low-viscosity hydrocarbons, so that their recovery is not worthwhile, or in which the low-viscosity hydrocarbons contained have been converted into higher-viscosity hydrocarbons

are, for example, by coking.

Thus, in a first variant for the treatment of the prepared rock masses or the residue masses by heating at atmospheric pressure of ground raw materials and possibly distilling off low viscosity

Hydrocarbons obtained. Increasing temperatures lead to an additional coking by thermolysis pyrolysis (T from RT to about 800 ° C), which significantly increases the C content.

Basically, the obtained low-viscosity

Hydrocarbons (petroleum) supplied to an external use or can also be used as an energy source for heating the masses.

In another variant, the processed

Rock masses or residue masses by gentle heating in vacuo and grinding of the starting materials and, if necessary

Distilling off low-viscosity hydrocarbons

receive. For example, it is possible to work with a negative pressure of up to 10 ^-3 mbar. This procedure has the

Advantage that a high proportion of hydrocarbons

can be distilled off and only small quantities of bitumen remain.

In yet another variant, the processed

Rock masses or residues by coking from Obtained starting materials in the closed space. In this case, substantially all low-viscosity hydrocarbons or petroleum components are pyrolyzed, so that the total carbon contained by the inventive

Method can be harnessed.

By the methods described above (pyrolysis,

Coking), therefore, the C content in the masses can be controlled (enriched). Preferably, however, as much oil as possible is recovered from the masses, so that only the

residual fraction of hydrocarbons for the

inventive method is used.

The invention is described below with reference to

Embodiments explained in detail.

example 1

9.2 g of finely ground oil sand (4 g content of pure Si0 ₂ ) whose C content according to residue analysis 0.037 g (= 8%) based on oil sand and 18.4% based on SiC-2, were

8.0 g of powdered activated carbon and 6 g of dextran added, pasted with a little water, granulated and dried in an oven at 100 ° C. The granules were densely packed in a quartz tube (inner diameter 22 mm) between two quartz wool plugs and annealed in a tube furnace at 800 ° C to remove residual water and add the dextran

pyrolyze. The temperature was then increased to 1300 ° C and a HCl gas stream of 4 1 / h through the package

passed. In the course of the reaction, the granules disintegrated into powdery material, which after 4 h reaction time a

Reduction of the amount of HCl gas to 3 1 / h required. The reaction gases were passed through a cold trap (-70 ° C)

to separate formed products from remaining HCl gas, H2, CO and CO2. After a reaction time of 12 hours, only residues of silicate material could still be found in the bed

Alkali / alkaline earth oxides and chlorides are detected. The isolated yield of SiCli was 9.23 g (81.6% of the theoretical yield, based on Si0 ₂ ). Thereafter, 4.1 g of AICI ₃ were separated by sublimation. Example 2

9.2 g of ground oil sand (residual content C: 8%, 18.4% based on 4 g of Si0 ₂ ) (average particle size 0.32 mm corresponding to a theoretical specific surface area of 75 cm ² / g), 8.2 g of powdered activated carbon and 6 g of dextran were treated as in Example 1, and the reaction was carried out similarly but at 1100 ° C. After 12 h reaction time, the reaction of Si0 ₂ ~ containing material was not yet

completed. The isolated yield of S1CI ₄ was 4.52 g (40% of the theoretical total conversion, based on S1O2).

In addition, AICI3 was isolated.

Example 3

9.15 g of oil sand (equivalent to 4 g of SiO 2) with 8 or 18.4% C coverage were admixed optionally with 16 g of ammonium fluoride (NH ₄ F) or 16 g of calcium difluoride (CaF 2), and 100 ml each were slowly added concentrated sulfuric acid (H ₂ S0) was added dropwise. Slowly heat the mixture to about 170 ° C

(over 4 h), 6.4 and 5.3 g of SiF _{4 were released} as gas and collected in a cooled to -196 ° C (liquid 2) cold trap. Yield: 77% and 64% of theory, respectively. SiF ₄ was characterized by ¹ H and ¹⁹ F NMR and GC / MS analysis.

Claims

claims

1. Process for producing tetrahalosilanes

(SiX ₄ ) (X = halogen, in particular Cl, F) from prepared, highly viscous hydrocarbons and rock masses containing S1O ₂ and / or silicates or in such a case

Preparation of residual masses in which the masses are heated in the hydrogen halide stream and the resulting SiX _{4 is} collected or distilled off.

2. The method according to claim 1, characterized

that the C content of the masses is determined.

3. A method according to claim 1 or 2, characterized in that carbon is added to the masses before or during the heating.

4. Method according to one of the preceding claims, characterized in that the masses for residual water removal to about 400-500 ° C and then to obtain SiX ₄ are heated to about 1000-1300 ° C.

5. Process for producing tetrahalosilanes

(SiX ₄ ) (X = halogen, in particular Cl, F) from prepared, highly viscous hydrocarbons and Si0 ₂ and / or silicates containing rock masses or those in such

Processing resulting residue compositions in which the masses are mixed with hydrofluoric acid (HF) and / or alkali or alkaline earth fluoride and sulfuric acid and the resulting SiX _{4 is} collected or distilled off.

6. The method according to any one of the preceding claims, characterized in that the processed rock masses

or residual masses by removal of rock in stone

contained oil, in particular via conventional mining and extraction methods, such as SAGD, CSS, THAI, VAPEX.

7. The method according to any one of claims 1 to 5, characterized characterized in that the processed rock masses or residue masses by heating at atmospheric pressure

obtained from ground raw materials and optionally distilling low-viscosity hydrocarbons.

8. The method according to any one of claims 1 to 5, characterized

characterized in that the processed rock masses

or residue masses are obtained by gentle heating in vacuo of ground raw materials and optionally distilling off low-viscosity hydrocarbons.

9. Method according to one of claims 1 to 5, characterized in that the processed rock masses or residue masses are obtained by coking of starting substances in the closed space.

10. Method according to one of the preceding claims, characterized in that as prepared rock masses or residue masses are used, which in the

Oil production from oil shales, oil sands, oil sludge

attack.