CN105502410A

CN105502410A - Preparation and purification methods of silicon tetrafluoride

Info

Publication number: CN105502410A
Application number: CN201510979401.0A
Authority: CN
Inventors: 蒋玉贵; 李翔宇; 孟祥军; 张净普; 胡帅; 朱文冬; 张长金
Original assignee: 718th Research Institute of CSIC
Current assignee: 718th Research Institute of CSIC
Priority date: 2015-12-23
Filing date: 2015-12-23
Publication date: 2016-04-20

Abstract

The invention relates to preparation and purification methods of silicon tetrafluoride and belongs to the field of fluorine chemical engineering and electronic industry gas. The preparation method comprises the step as follows: a silicon-containing substance and a fluorine-containing substance are mixed to react to produce silicon tetrafluoride. The purification method comprises steps as follows: the to-be-purified coarse product, namely, silicon tetrafluoride, and a reactive material for purification react to produce coarse product Mm(SiF6)p or Mn(HSiF6)q, then thermal decomposition is performed, and purified silicon tetrafluoride is obtained. With the adoption of the preparation method, no acid or corrosive liquid substances are used, the silicon-containing substance and the fluorine-containing substance, particularly a gaseous fluorine-containing substance, react to produce silicon tetrafluoride, fewer impurities are introduced, the purity of the product silicon tetrafluoride is higher, the preparation method has the advantages of high safety, simplicity in operation, high yield, economy and the like, fewer waste acid and residues can be produced, and environmental pollution is lower; with the adoption of the purification method, high-purity silicon tetrafluoride gas can be obtained, and the content of impurity (SiF3)2O and HF is extremely low.

Description

A kind of preparation of silicon tetrafluoride and purification process

Technical field

The present invention relates to a kind of preparation and purification process of silicon tetrafluoride, belong to fluorine chemical, electronic industry gas field.

Background technology

Silicon tetrafluoride (SiF ₄) in electronics and semicon industry, be mainly used in the etching reagent, P-type dopant, epitaxial deposition diffuse si source etc. of silicon nitride, tantalum silicide etc., also can be used for preparing electronic-grade silane or silicon.Silicon tetrafluoride also can be used as the raw material of photoconductive fiber pure quartz glass, and it is hydrolyzed the heat sink SiO that can produce and have high-specific surface area in thermal-flame ₂.In addition, silicon tetrafluoride is also widely used in the stiffening agent etc. preparing solar cell, silicofluoric acid and aluminum fluoride, chemical analysis, fluorizating agent, oil well probing, magnesium alloy casting, catalyzer, fumigant, cement and artificial marble.Use silicon tetrafluoride in pre-cast concrete after, its solidity to corrosion and wear resistance can be promoted, improve its porosity and increase compressive strength.

Scheele in 1771, by the reaction of hydrofluoric acid and silicon-dioxide, makes silicon tetrafluoride first.Up to now, the preparation method of silicon tetrafluoride is generally following several:

(1) fluorite sulfuric acid reaction prepares silicon tetrafluoride, and chemical equation is as follows:

2CaF ₂+2H ₂SO ₄+SiO ₂→2CaSO ₄+SiF ₄+2H ₂O；

Water (H is had in the production process of this method ₂o) generate, the silicon tetrafluoride (SiF obtained ₄) gas can rapidly and water to react generation Si oxide, easily cause silicon tetrafluoride to be hydrolyzed, and introduce (SiF ₃) ₂the impurity such as O and HF, thus the purity affecting silicon tetrafluoride gas.The plurality of impurities contained in fluorite, also will be brought in silicon tetrafluoride, will affect silicon tetrafluoride purity; Wherein, silicon tetrafluoride (SiF ₄) chemical equation that reacts of gas and water is as follows:

2SiF ₄+H ₂O→(SiF ₃) ₂O+2HF；

Described method weak point is: reactant is the mixture of many kinds of substance, composition more complicated, the silicon tetrafluoride impurity of output is many, remove impurity wherein, input cost compare is high, and also discontinuous is produced, therefore production capacity is lower, the solid product of output, acidity is larger, and resultant not easily processes; Environmental pollution is more serious.

(2) silicofluoride or silicofluoric acid and strong sulfuric acid response prepare silicon tetrafluoride:

Chemical equation is exemplified below:

CaSiF ₆+H ₂SO ₄→SiF ₄+CaSO ₄+2HF；

H ₂SiF ₆+H ₂SO ₄→SiF ₄+H ₂SO ₄+2HF；

The product that described method obtains is vitriol, silicon tetrafluoride gas and hydrofluoric acid (HF), because mostly reactant silicofluoride and silicofluoric acid are the byproduct in Rock Phosphate (72Min BPL) or Phosphate Fertilizer Industry production process, therefore containing plurality of impurities, to be brought in product silicon tetrafluoride, silicon tetrafluoride purity will be affected.

(3) thermal decomposition method prepares silicon tetrafluoride:

Produce the thermal decomposition method of silicon tetrafluoride refer to higher than under heat decomposition temperature to metal fluorosilicates, such as Na ₂siF ₆, BaSiF ₆etc. carrying out thermolysis.Described method need be heat-treated and silicofluoride is dewatered, and the silicon tetrafluoride of production has very high purity and productive rate.But thermal decomposition product such as NaF, KF etc. are easy to invest furnace wall, and observable index is comparatively large, has crystal water to exist, easily causes the generation of other impurity.

Chemical equation is exemplified below:

Na ₂SiF ₆→SiF ₄+2NaF；

Except above-mentioned three kinds of silicon tetrafluoride preparation methods, in prior art, also comprise following preparation method:

Be disclosed in Chinese patent CN200580027190 in the torch of plasma reactor, by silicon-dioxide (SiO ₂) at 1100 DEG C ~ 1200 DEG C, use element fluorine F ₂fluoridize production silicon tetrafluoride.This patent prepared by the torch of plasma reactor, its application of special device-restrictive.

In the preparation method of above-mentioned several silicon tetrafluorides, there is more shortcoming, such as: use starting material impurity more, use acidic substance HF, H ₂sO ₄, H ₂siF ₆there is larger danger, particularly HF there is larger corrosion risk, produce water after production process or form HF spent acid, H ₂sO ₄spent acid, H ₂siF ₆spent acid difficult treatment, thermolysis production unit NaF, KF invest furnace wall, or use plasma reactor specific installation.In sum, the defect easily introduced plurality of impurities and cause product silicon tetrafluoride purity drop is there is in the preparation method of prior art silicon tetrafluoride, for meeting Production requirement, urgently a kind of easy acquisition high purity, high security, high yield, economically prepare the method for silicon tetrafluoride.

Summary of the invention

In view of this, an object of the present invention is the preparation method providing a kind of silicon tetrafluoride, and described preparation method avoids using hydrofluoric acid or hydrogen fluoride (HF), sulfuric acid (H ₂sO ₄), silicofluoric acid (H ₂siF ₆) etc. acid and corrodibility fluent meterial, by using the fluorine-containing material of silicon-containing material and fluorine-containing material especially gaseous state, silicon tetrafluoride is prepared in reaction, it is less that described preparation method introduces impurity, obtained product silicon tetrafluoride purity is higher, there is the advantage that security is high, simple to operate, productive rate is high and more economical, less useless diluted acid HF, H can be produced ₂sO ₄, H ₂siF ₆and waste residue, environmental pollution is smaller.

Two of object of the present invention is the purification process providing a kind of silicon tetrafluoride, and described purification process can obtain high purity and obtain silicon tetrafluoride gas, wherein impurity (SiF ₃) ₂o and HF content is extremely low.

The object of the invention is to be achieved through the following technical solutions.

A preparation method for silicon tetrafluoride, described preparation method's step comprises:

Silicon-containing material is mixed with fluorine-containing material and reacts, prepare silicon tetrafluoride;

Wherein, described silicon-containing material is silicon (Si), silane (SiH ₄), silicon-dioxide (SiO ₂), silica gel (mSiO ₂nH ₂o), metal silicide, trichlorosilane (SiHCl ₃), dichloro hydrogen silicon (SiH ₂cl ₂), a chlorine hydrogen silicon (SiH ₃cl), silicon tetrachloride (SiCl ₄), silicon bromide (SiBr ₄), iodate silicon (SiI ₄), silicon nitride (Si ₃n ₄), silicon carbide (SiC), silicon boride (SiB ₆) and silicon sulfide (SiS ₂) in more than one;

Described fluorine-containing material is nitrogen trifluoride (NF ₃), fluorine gas (F ₂), carbonyl fluoride (COF ₂), chlorine trifluoride (ClF ₃) and chlorine monofluoride (ClF) in more than one;

For different silicon-containing materials and fluorine-containing material, reaction pressure is ﹣ 0.09MPa ~ 5MPa, and temperature of reaction is as follows respectively:

(1), when silicon-containing material is silicon-dioxide, when fluorine-containing material is nitrogen trifluoride, temperature of reaction is 701 DEG C ~ 3999 DEG C;

(2), when silicon-containing material is silicon-dioxide, when fluorine-containing material is fluorine gas, temperature of reaction is 2001 DEG C ~ 3999 DEG C;

(3), except (1) and (2), when other silicon-containing material and fluorine-containing material, temperature of reaction is ﹣ 49 DEG C ~ 3999 DEG C.

Preferred described silicon-containing material is the silicon-containing material after purifying, be more preferably the silicon-containing material of purity >=99.9%, by this area conventional purification method such as washing, drying, recrystallization and/or filtrations, purifying is carried out to described silicon-containing material, remove dust wherein and other gaseous impuritieies.

Preferred described fluorine-containing material is the fluorine-containing material after purifying, is more preferably the fluorine-containing material of purity >=99.9%, carries out purifying by this area conventional purification method such as distillation or rectifying to described fluorine-containing material.

Fluorine atom in preferred fluorine-containing material is 0.025 ~ 40:1 with the ratio of the amount of substance of the Siliciumatom in silicon-containing material.

Preferred reaction pressure is ﹣ 0.05MPa ~ 1MPa, is more preferably 0.05MPa ~ 0.5MPa.

For different silicon-containing materials and fluorine-containing material, temperature of reaction is preferably as follows respectively:

(1) when silicon-containing material is silicon-dioxide, when fluorine-containing material is nitrogen trifluoride, preferable reaction temperature is 701 DEG C ~ 3499 DEG C, is more preferably 851 DEG C ~ 2999 DEG C, most preferably is 1001 DEG C ~ 2699 DEG C;

(2) when silicon-containing material is silicon-dioxide, when fluorine-containing material is fluorine gas, preferable reaction temperature is 2051 DEG C ~ 3499 DEG C, is more preferably 2101 DEG C ~ 2999 DEG C, most preferably is 2501 DEG C ~ 2699 DEG C;

(3) except (1) and (2), when other silicon-containing material and fluorine-containing material, preferable reaction temperature is 1 DEG C ~ 1499 DEG C, is more preferably 1 DEG C ~ 999 DEG C, most preferably is 51 DEG C ~ 499 DEG C.

After preferably silicon-containing material and fluorine-containing material being reacted, collected the silicon tetrafluoride prepared by cryotrap.

Preferred described preparation method adds diluent media and dilutes; Described diluent media is nitrogen (N ₂), air, helium (He) and silicon tetrafluoride (SiF ₄) at least one; Be silicon-containing material and/or fluorine-containing material by diluent materials.

Described diluent media can add before silicon-containing material and fluorine-containing material mixing, at least one party in dilution silicon-containing material or fluorine-containing material, or adds and dilute after silicon-containing material and fluorine-containing material mixing.

Preferred described preparation method uses catalyzer, and described catalyzer is at least one in the metal fluoride of the metal fluoride of silver, the metal fluoride of cobalt, the metal fluoride of manganese, the metal fluoride of tin and cerium.

A purification process for silicon tetrafluoride, described method comprises:

Crude product silicon tetrafluoride to be purified and purifying reactive material are reacted and prepares crude product silicofluoride (M _m(SiF ₆) _p) or crude product hydrofluosilicate (M _n(HSiF ₆) _q), crude product silicofluoride or crude product hydrofluosilicate are carried out thermolysis, obtains the silicon tetrafluoride of purifying.

Wherein, crude product silicon tetrafluoride to be purified can adopt existing silicon tetrafluoride preparation method to prepare, prepare silicon tetrafluoride, silicofluoride or silicofluoric acid as fluorite sulfuric acid reaction and strong sulfuric acid response prepares silicon tetrafluoride, thermal decomposition method prepares silicon tetrafluoride or fluoridized with element fluorine at 1100 DEG C ~ 1200 DEG C by silicon-dioxide in the torch of plasma reactor and produce silicon tetrafluoride etc., the preparation method of a kind of silicon tetrafluoride of the present invention also can be adopted to prepare; Purity >=60% of crude product silicon tetrafluoride preferably to be purified; Crude product silicon tetrafluoride to be purified also can first by freezing vacuumize carry out preliminary purification after, then to react with purifying reactive material.

Purifying reactive material is fluorochemical (MF _x), hydrofluoride (M (HF ₂) _y), hydrogen fluoride (HF) and ammonia (NH ₃) at least one, when purifying reactive material is hydrogen fluoride (HF), fluorochemical (MF should be contained at least simultaneously _x); When purifying reactive material is ammonia (NH ₃) time, should contain hydrogen fluoride (HF), described M is metal or NH at least simultaneously ₄, F is fluorine atom, HF ₂for hydrogen fluorine root, x is the number of F, and 1≤x, y are HF ₂number, 1≤y, SiF ₆for silicofluoric acid root, HSiF ₆for hydrofluosillicic acid root, m is M _m(SiF ₆) _pthe number of middle M, 1≤m, n are M _n(HSiF ₆) _qthe number of middle M, 1≤n, p are SiF ₆number, 1≤p, q are HSiF ₆number, 1≤q.

The temperature that crude product silicon tetrafluoride to be purified and purifying reactive material are reacted is preferably-99 DEG C ~ 999 DEG C, and reaction pressure is preferably ﹣ 0.09MPa ~ 2MPa.

Crude product silicofluoride is preferably (NH ₄) ₂siF ₆, FeSiF ₆, CuSiF ₆, CoSiF ₆or CrSiF ₆, crude product hydrofluosilicate is preferably NH ₄hSiF ₆, LiHSiF ₆, NaHSiF ₆, KHSiF ₆or CsHSiF ₆.

Crude product silicofluoride or crude product hydrofluosilicate being carried out the preferred heat decomposition temperature of thermolysis is 51 DEG C ~ 1999 DEG C, and more preferably heat decomposition temperature is 201 DEG C ~ 999 DEG C; Most preferably heat decomposition temperature is 301 DEG C ~ 499 DEG C; Preferred thermolysis pressure is ﹣ 0.09MPa ~ 5MPa, more preferably thermolysis pressure 0.05MPa ~ 0.5MPa.

Preferably before thermolysis, this area conventional purification method is adopted to carry out purifying to crude product silicofluoride or crude product hydrofluosilicate, as dissolution filter, recrystallization, drying and/or vacuumize.

Preferably before thermolysis, carry out heat pre-treatment to crude product silicofluoride or crude product hydrofluosilicate, can obtain a small amount of silicon tetrafluoride, this part silicon tetrafluoride is not collected, as three-protection design or recycling; Preferred heat pre-treatment temperature is 51 DEG C ~ 1999 DEG C, and preferred heat pre-treatment pressure is-0.09MPa ~ 0.5MPa.

Preferably vacuumized before thermolysis, vacuum tightness reaches≤-0.099MPa, to remove the gaseous impuritieies such as oxygen, nitrogen and carbonic acid gas.

Preferably the purifying silicon tetrafluoride gas obtained after thermolysis is passed into cold-trap, be conducive to heavy constituent impurity to stay in cold-trap to remove, collect and obtain the higher silicon tetrafluoride gas of purity.

By the silicon tetrafluoride that the preparation method of a kind of silicon tetrafluoride of the present invention prepares, and the high-purity silicon tetrafluoride that the purification process purifying of a kind of silicon tetrafluoride of the present invention obtains, its purposes is not particularly limited, in the multiple Application Areas that background technology used in the present invention is introduced.

Wherein, the silicon tetrafluoride purity obtained due to described purification process purifying is high, be specially adapted to the film forming gas of semiconductor-fabricating device, etching reagent, the P-type dopant and epitaxial deposition diffuse si source etc. of silicon nitride, tantalum silicide etc. is mainly used in, for the preparation of electronic-grade silane or silicon in electronics and semicon industry.

The pressure that the present invention relates to, if without specified otherwise, all refers to gauge pressure.

Beneficial effect

1. the invention provides a kind of preparation method of silicon tetrafluoride, described preparation method uses silicon-containing material and fluorine-containing material to react to prepare silicon tetrafluoride, especially the fluorine-containing material of gas, have selected favourable reaction conditions, as temperature, pressure, silicon tetrafluoride is prepared in reaction, due at least one raw material in described preparation method, major part does not contain H or O atom, in most cases, anhydrous generation in product, will avoid silicon tetrafluoride to be hydrolyzed and introduce (SiF ₃) ₂the impurity such as O and HF, even if before reaction there is a small amount of impurity, especially (SiF in silicofluoride or hydrofluosilicate ₃) ₂o, fluorine-containing material also will react with it and generate SiF ₄, then generate silicon tetrafluoride by thermolysis, decrease foreign matter content, provide SiF ₄productive rate; Avoid using the acid and corrodibility fluent meterial such as hydrofluoric acid or hydrogen fluoride, sulfuric acid, silicofluoric acid, reaction residual without remaining spent acid or waste residue, as HF, H ₂sO ₄, H ₂siF ₆etc., more easily process, environmental pollution is smaller; The product silicon tetrafluoride less introducing impurity that described preparation method obtains, purity are higher, have the advantage that security is high, simple to operate, productive rate is high and more economical;

2. the invention provides a kind of preparation method of silicon tetrafluoride, described preparation method also can add diluent media and dilute, and by improving the security of reaction, makes reacting balance; Described preparation method also can use catalyst to react, and uses catalyzer, and will improve the security of reaction, make reacting balance, in addition, catalyzer can also add fast response, reduces the reaction times;

3. the invention provides a kind of purification process of silicon tetrafluoride, described purification process is by by crude product silicon tetrafluoride to be purified and purifying reactive material, the obtained crude product silicofluoride of reaction or crude product hydrofluosilicate, through dissolution filter, recrystallization, drying, the purifying such as to vacuumize and obtain high-purity fluorine silicate, then thermolysis obtains high-purity silicon tetrafluoride gas, wherein, pass through to select applicable silicofluoride or hydrofluosilicate, especially (NH in thermolysis ₄) ₂siF ₆, NH ₄hSiF ₆thermal decomposition product thermal decomposition method in prior art can being avoided to prepare mention in silicon tetrafluoride as NaF, KF etc. be easy to invest furnace wall, observable index comparatively large, have crystal water to there is, cause the problems such as the generation of other impurity, convenient purifying easily obtains silicon tetrafluoride, (NH ₄) ₂siF ₆, NH ₄hSiF ₆thermolysis obtains NH ₃, HF and SiF ₄, NH ₃boiling point be-33.43 DEG C, the boiling point of silicon tetrafluoride-94.8 DEG C, both be easier to be separated, the purity of silicon tetrafluoride can't be affected; Meanwhile, before thermolysis, carry out heat pre-treatment, be conducive to obtaining the higher silicon tetrafluoride gas of purity.

Embodiment

The device used in following examples 1 ~ 82 is as follows:

A kind of preparation facilities of silicon tetrafluoride, described preparation facilities is made up of Monel metal, the reaction chamber of described preparation facilities has 10L volume, heating watt is furnished with in the outside of described preparation facilities, the reaction chamber diameter of described preparation facilities is 100mm, silicon-containing material is added in reaction chamber described in reaction forward direction, fluorine-containing material and silicon-containing material mixing is passed into by inlet pipe, when needing to add diluent media, added by diluent media pipe, add when silicon-containing material and fluorine-containing material mixing and dilute, in a heated condition, silicon-containing material and fluorine-containing material react, react the crude product silicon tetrafluoride gas prepared and pass through escape pipe, enter follow-up cold-trap collection and prepare silicon tetrafluoride.

A kind of purification devices of silicon tetrafluoride, described purification devices and being made up of Monel metal, the reaction chamber of described purification devices has 5L volume, heating watt is furnished with in the outside of described purification devices, described reaction chamber diameter is 100mm, purifying reactive material is added in reaction chamber described in reaction forward direction, silicon tetrafluoride raw gas is passed into by inlet pipe, react and prepare crude product silicofluoride or crude product hydrofluosilicate, again successively through filtering, recrystallization and drying, obtain silicofluoride or hydrofluosilicate, in described purification devices, by vacuumizing removing oxygen, the gaseous impurities such as nitrogen and carbonic acid gas, heating silicofluoride or hydrofluosilicate carry out thermolysis, the high-purity silicon tetrafluoride gas that purifying obtains passes through escape pipe, enter the silicon tetrafluoride fine work gas that follow-up cold-trap collection purifying obtains, a small amount of heavy constituent impurity will be stayed in cold-trap, highly purified silicon tetrafluoride is stored to product storage tank.

Productive rate refers to the actual output of certain resultant and the ratio of theoretical yield, the calculating of productive rate, calculate with raw material in shortage, such as silicon-containing material and fluorine-containing material react according to the ratio of certain amount of substance, if silicon-containing material is in shortage, productive rate calculates with silicon-containing material, if fluorine-containing material is in shortage, productive rate calculates with fluorine-containing material.

Detecting instrument and the testing conditions of the silicon tetrafluoride gas in following examples 1 ~ 82 are as follows:

For the gas of purity < 99.9%, gas is imported Shimadzu GC-14C model gas chromatograph, analytical gas forms.Be silicon tetrafluoride by the main component of gas chromatograph determination gas, gas Chromatographic Determination uses helium as carrier gas, use TCD detector, flow rate of carrier gas is 100mL/min, column temperature is 40 DEG C, injector temperature is 100 DEG C, and TCD temperature is 100 DEG C, and the maximum peak in gas-chromatography is the chromatographic peak of silicon tetrafluoride.According to the integral area of the silicon tetrafluoride of data from gas chromatography result and the chromatographic peak of various impurity, calculate the purity of various foreign matter content and silicon tetrafluoride respectively.

Gas for purity >=99.9% is undertaken qualitative by GC-9560 helium ion gas chromatograph, determine that the main component of described gas is silicon tetrafluoride, carry out quantitatively mainly through gas chromatograph, calculate the content of each impurity according to the integral area data of the chromatographic peak of impurity each in data from gas chromatography result, then calculate the purity of silicon tetrafluoride.

Conveniently read, the ratio of the amount of substance of the Siliciumatom in silicon-containing material " fluorine atom in fluorine-containing material with " is in the examples below referred to as " fluorine silicon than ".

Embodiment 1

(1) by the AgF of 200g drying ₂put into the reaction chamber of dry silicon tetrafluoride preparation facilities as catalyzer, add the silicon-containing material Si of 200g drying, supply dry fluorine-containing material F by the inlet pipe of described preparation facilities to reaction chamber ₂start reaction, fluorine silicon is than being 40:1, and in reaction chamber, temperature of reaction is 51 DEG C, and reaction pressure is-0.05MPa; Derive reaction product from the air outlet of described preparation facilities, pass into the cryotrap of-110 DEG C, collect the gas prepared;

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 21%.

(2) crude product silicon tetrafluoride to be purified is passed into silicon tetrafluoride purification devices, with purifying reactive material fluorochemical NH ₄it is crude product (NH that F reaction prepares crude product silicofluoride ₄) ₂siF ₆, by crude product (NH ₄) ₂siF ₆by filter paper filtering except impurity such as dusts, recrystallization in water, is then evacuated to-0.09MPa and is heated to 50 DEG C and carry out drying, and obtaining the silicofluoride after purifying is (NH ₄) ₂siF ₆, then in described purification devices, carry out heat pre-treatment, heat pre-treatment temperature is 1999 DEG C, heat pre-treatment pressure is 0.5MPa, then vacuumizes, and makes pressure to-0.099MPa, the gaseous impuritieies such as removing oxygen, nitrogen, carbonic acid gas, finally carry out thermolysis, heat decomposition temperature is 1999 DEG C, and thermolysis pressure is 5MPa, obtain high purity and obtain silicon tetrafluoride gas, by the escape pipe of described purification devices, enter the cold-trap of-110 DEG C, collect and obtain the higher purified gases of purity;

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 2

(1) do not use catalyzer, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and diluent media is N ₂, temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 98%, and productive rate is 97%.

(2) crude product silicon tetrafluoride to be purified is passed into silicon tetrafluoride purification devices, with purifying reactive material hydrofluoride NaHF ₂it is crude product NaHSiF that reaction prepares crude product hydrofluosilicate ₆, by crude product NaHSiF ₆by filter paper filtering except impurity such as dusts, recrystallization in water, is then evacuated to-0.09MPa and is heated to 50 DEG C of dryings, and obtaining the hydrofluosilicate after purifying is NaHSiF ₆, then in described purification devices, carry out heat pre-treatment, heat pre-treatment temperature is 1999 DEG C, heat pre-treatment pressure is 0.5MPa, then vacuumizes, and makes pressure to-0.099MPa, the gaseous impuritieies such as removing oxygen, nitrogen, carbonic acid gas, finally carry out thermolysis, heat decomposition temperature is 1999 DEG C, and thermolysis pressure is 5MPa, obtain highly purified silicon tetrafluoride gas, by the escape pipe of described purification devices, enter the cold-trap of-110 DEG C, collect and obtain the higher purified gases of purity;

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.99%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 3

(1) do not use catalyzer, fluorine-containing material is ClF ₃, fluorine silicon is than being 20:1, and temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 9%.

(2) purifying reactive material is fluorochemical FeF ₂, crude product silicofluoride is crude product FeSiF ₆, silicofluoride is FeSiF ₆, heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 1 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.999%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 4

(1) catalyzer is CeF ₃, fluorine-containing material is ClF, and fluorine silicon is than being 10:1, and diluent media is SiF ₄, temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 6%.

(2) heat pre-treatment temperature is 1999 DEG C, and heat pre-treatment pressure is 0.5MPa, and heat decomposition temperature is 1999 DEG C, and thermolysis pressure is 5MPa, and all the other are with embodiment 3 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.9%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 5

(1) do not use catalyzer, fluorine-containing material is NF ₃, fluorine silicon is than being 1:1, and diluent media is air, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 93%, and productive rate is 91%.

(2) heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 2 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.9%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 6

(1) silicon-containing material is SiH ₄, diluent media is He, and temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 8%.

(2) purifying reactive material is hydrofluoride LiHF ₂, crude product hydrofluosilicate is crude product LiHSiF ₆, hydrofluosilicate is LiHSiF ₆, all the other are with embodiment 2 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.9%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 7

(1) do not use catalyzer, silicon-containing material is SiH ₄, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 85%, and productive rate is 81%.

(2) purifying reactive material is fluorochemical CoF ₂, crude product silicofluoride is crude product CoSiF ₆, silicofluoride is CoSiF ₆, all the other are with embodiment 3 step (2);

Embodiment 8

(1) catalyzer is CoF ₃, silicon-containing material is SiH ₄, fluorine-containing material is ClF ₃, fluorine silicon is than being 4:1, and diluent media is SiF ₄, temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) purifying reactive material is fluorochemical CoF ₂, crude product silicofluoride is crude product CoSiF ₆, silicofluoride is CoSiF ₆, all the other are with embodiment 1 step (2);

Embodiment 9

(1) catalyzer is CeF ₃, silicon-containing material is SiH ₄, fluorine-containing material is ClF, and fluorine silicon is than being 0.5:1, and diluent media is SiF ₄, temperature of reaction is 1 DEG C, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 15%.

(2) purifying reactive material is fluorochemical CrF ₂, crude product silicofluoride is crude product CrSiF ₆, silicofluoride is CrSiF ₆, heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 1 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.9%, impurity (SiF ₃) ₂o content < 1ppm, HF content < 1ppm, F ₂content < 1ppm.

Embodiment 10

(1) catalyzer is MnF ₂, silicon-containing material is SiH ₄, fluorine-containing material is NF ₃, fluorine silicon is than being 0.3:1, and temperature of reaction is 1001 DEG C, and all the other are with embodiment 1 step (1);

(2) purifying reactive material is fluorochemical CrF ₂, crude product silicofluoride is crude product CrSiF ₆, silicofluoride is CrSiF ₆, all the other are with embodiment 1 step (2);

Embodiment 11

(1) silicon-containing material is SiO ₂, fluorine silicon is than being 5:1, and diluent media is N ₂, temperature of reaction is 2001 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 89%, and productive rate is 80%.

(2) heat pre-treatment temperature is 51 DEG C, and pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and pressure is-0.09MPa, and all the other are with embodiment 1 step (2);

Embodiment 12

(1) do not use catalyzer, silicon-containing material is SiO ₂, fluorine-containing material is COF ₂, fluorine silicon is than being 1:7, and temperature of reaction is 200 DEG C, and reaction pressure is 0.1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 82%, and productive rate is 80%.

(2) purifying reactive material is hydrofluoride NH ₄hF ₂, crude product hydrofluosilicate is crude product NH ₄hSiF ₆, hydrofluosilicate is NH ₄hSiF ₆, all the other are with embodiment 2 step (2);

Embodiment 13

(1), catalyzer is CoF ₃, silicon-containing material is SiO ₂, fluorine-containing material is ClF ₃, fluorine silicon is than being 1:1, and diluent media is N ₂, temperature of reaction is 2999 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 92%, and productive rate is 90%.

(2) with embodiment 3 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.999%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 14

(1) catalyzer is CeF ₃, silicon-containing material is SiO ₂, fluorine-containing material is ClF, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 98%, and productive rate is 90%.

(2) with embodiment 4 step (2);

Embodiment 15

(1) catalyzer is MnF ₂, silicon-containing material is SiO ₂, fluorine-containing material is NF ₃, fluorine silicon is than being 0.025:1, and diluent media is SiF ₄, temperature of reaction is 701 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 55%.

(2) with embodiment 3 step (2);

Embodiment 16

(1) do not use catalyzer, silicon-containing material is SiO ₂, fluorine silicon is than being 5:1, and temperature of reaction is 2699 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 80%.

(2) with embodiment 1 step (2);

Embodiment 17

(1) do not use catalyzer, silicon-containing material is SiO ₂, fluorine silicon is than being 7:1, and diluent media is N ₂, temperature of reaction is 3999 DEG C, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 85%.

(2) with embodiment 11 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 98%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 18

(1) catalyzer is CoF ₃, silicon-containing material is SiO ₂, fluorine silicon is than being 0.025:1, and diluent media is N ₂, temperature of reaction is 2051 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 1 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 97%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 19

(1) catalyzer is CeF ₃, silicon-containing material is SiO ₂, fluorine-containing material is NF ₃, diluent media is N ₂, temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 89%, and productive rate is 88%.

(2) with embodiment 11 step (2);

Embodiment 20

(1) silicon-containing material is SiO ₂, fluorine silicon is than being 0.2:1, and diluent media is SiF ₄, temperature of reaction is 2501 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 12 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 96%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 21

(1) catalyzer is SnF ₂, silicon-containing material is SiO ₂, fluorine silicon is than being 30:1, and diluent media is air, and temperature of reaction is 3499 DEG C, and reaction pressure is 0.05MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 89%, and productive rate is 84%.

(2) purifying reactive material is hydrofluoride NH ₄hF ₂, crude product hydrofluosilicate is crude product NH ₄hSiF ₆, silicofluoride is NH ₄hSiF ₆, heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 2 step (2);

Embodiment 22

(1) catalyzer is MnF ₂, silicon-containing material is SiO ₂, fluorine silicon is than being 20:1, and diluent media is SiF ₄, temperature of reaction is 2999 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 85%, and productive rate is 82%.

(2) with embodiment 12 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99%, impurity (SiF ₃) ₂o content < 1ppm, HF content < 1ppm, F ₂content < 1ppm.

Embodiment 23

(1) silicon-containing material is silica gel, and fluorine silicon is than being 1:2, and diluent media is air, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 98%, and productive rate is 85%.

(2) with embodiment 11 step (2);

Embodiment 24

(1) do not use catalyzer, silicon-containing material is silica gel, and fluorine-containing material is COF ₂, temperature of reaction is 1 DEG C, and reaction pressure is 0.05MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 12%.

(2) purifying reactive material is hydrofluoride KHF ₂, crude product hydrofluosilicate is crude product KHSiF ₆, silicofluoride is KHSiF ₆, all the other are with embodiment 2 step (2);

Embodiment 25

(1) catalyzer is SnF ₂, silicon-containing material is silica gel, and fluorine-containing material is ClF ₃, fluorine silicon is than being 0.025:1, and diluent media is SiF, and temperature of reaction is 1001 DEG C, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 95%, and productive rate is 88%.

(2) with embodiment 3 step (2);

Embodiment 26

(1) catalyzer is CeF ₃, silicon-containing material is silica gel, and fluorine-containing material is ClF, and fluorine silicon is than being 0.1:1, and diluent media is SiF ₄, temperature of reaction is 1499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 88%, and productive rate is 87%.

(2) with embodiment 4 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 27

(1) catalyzer is MnF ₂, silicon-containing material is silica gel, and fluorine-containing material is NF ₃, diluent media is SiF ₄, temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 7%.

(2) with embodiment 3 step (2);

Embodiment 28

(1) do not use catalyzer, silicon-containing material is Mg ₂si, fluorine silicon is than being 20:1, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 38%.

(2) with embodiment 1 step (2);

Embodiment 29

(1) do not use catalyzer, silicon-containing material is Ca ₂si, fluorine-containing material is COF ₂, fluorine silicon is than being 1:7, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 21 step (2);

Embodiment 30

(1) catalyzer is CoF ₃, silicon-containing material is Fe ₂si, fluorine-containing material is ClF ₃, fluorine silicon is than being 0.1:1, and diluent media is SiF ₄, temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 37%.

(2) with embodiment 4 step (2);

Embodiment 31

(1) catalyzer is CeF ₃, silicon-containing material is Fe ₂si, fluorine-containing material is ClF, and fluorine silicon is than being 1:10, and diluent media is SiF ₄, temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 3 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.999%, impurity (SiF ₃) ₂o content < 1ppm, HF content < 1ppm, F ₂content < 1ppm.

Embodiment 32

(1) catalyzer is MnF ₂, silicon-containing material is Zn ₂si, fluorine-containing material is NF ₃, fluorine silicon is than being 0.025:1, and temperature of reaction is 1 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 4 step (2);

Embodiment 33

(1) silicon-containing material is SiHCl ₃, diluent media is N ₂, temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 89%.

(2) with embodiment 11 step (2);

Embodiment 34

(1) do not use catalyzer, silicon-containing material is SiHCl ₃, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and temperature of reaction is 1001 DEG C, and reaction pressure is 0.05MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 87%.

(2) with embodiment 24 step (2);

Embodiment 35

(1) catalyzer is CoF ₃, silicon-containing material is SiHCl ₃, fluorine-containing material is ClF ₃, fluorine silicon is than being 1:3, and diluent media is SiF ₄, temperature of reaction is 1499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 91%, and productive rate is 90%.

(2) with embodiment 3 step (2);

Embodiment 36

(1) catalyzer is CeF ₃, silicon-containing material is SiHCl ₃, fluorine-containing material is ClF, and fluorine silicon is than being 20:1, and diluent media is air, and temperature of reaction is 2999 DEG C, and reaction pressure is 3MPa, and all the other are with embodiment 1 step (1);

(2) purifying reactive material is fluorochemical CuF ₂, crude product silicofluoride is crude product CuSiF ₆, silicofluoride is CuSiF ₆, all the other are with embodiment 1 step (2);

Embodiment 37

(1) catalyzer is MnF ₂, silicon-containing material is SiHCl ₃, fluorine-containing material is NF ₃, fluorine silicon is than being 0.4:1, and diluent media is He), temperature of reaction is 1999 DEG C, and reaction pressure is 2MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 7 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 98%, impurity (SiF ₃) ₂o content < 0.01ppm, HF content < 0.01ppm, F ₂content < 0.01ppm.

Embodiment 38

(1) silicon-containing material is SiH ₂cl ₂, fluorine silicon is than being 1:1, and temperature of reaction is 800 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 1 step (2);

Embodiment 39

(1) do not use catalyzer, silicon-containing material is SiH ₂cl ₂, fluorine-containing material is COF ₂, fluorine silicon is than being 1:1, and temperature of reaction is 700 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 89%, and productive rate is 87%.

(2) with embodiment 21 step (2);

Embodiment 40

(1) catalyzer is CoF ₃, silicon-containing material is SiH ₂cl ₂, fluorine-containing material is ClF ₃, fluorine silicon is than being 3:1, and temperature of reaction is 600 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 4 step (2);

Embodiment 41

(1) catalyzer is CeF ₃, silicon-containing material is SiH ₂cl ₂, fluorine-containing material is ClF, and fluorine silicon is than being 1:6, and diluent media is SiF ₄, temperature of reaction is-10 DEG C, and reaction pressure is 0.2MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 3 step (2);

Embodiment 42

(1) do not use catalyzer, silicon-containing material is SiH ₂cl ₂, fluorine-containing material is NF ₃, fluorine silicon is than being 20:1, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 8 step (2);

Embodiment 43

(1) catalyzer is SnF ₂, silicon-containing material is SiH ₃cl, temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 89%, and productive rate is 86%.

(2) with embodiment 11 step (2);

Embodiment 44

(1) do not use catalyzer, silicon-containing material is SiH ₃cl, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and temperature of reaction is 1001 DEG C, and all the other are with embodiment 1 step (1);

(2) with embodiment 6 step (2);

Embodiment 45

(1) catalyzer is CoF ₃, silicon-containing material is SiH ₃cl, fluorine-containing material is ClF ₃, fluorine silicon is than being 20:1, and diluent gas is He, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 3 step (2);

Embodiment 46

(1) catalyzer is CeF ₃, silicon-containing material is SiH ₃cl, fluorine-containing material is ClF, and fluorine silicon is than being 1:1, and temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 88%.

(2) with embodiment 36 step (2);

Embodiment 47

(1) catalyzer is MnF ₂, silicon-containing material is SiH ₃cl, fluorine-containing material is NF ₃, fluorine silicon is than being 1:9, and diluent media is N ₂, temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 7 step (2);

Embodiment 48

(1) do not use catalyzer, silicon-containing material is SiCl ₄, fluorine silicon is than being 4:1, and temperature of reaction is 999 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 1 step (2);

Embodiment 49

(1) do not use catalyzer, silicon-containing material is SiCl ₄, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and temperature of reaction is 1 DEG C, and all the other are with embodiment 1 step (1);

(2) with embodiment 21 step (2);

Purified gases is detected, known: purified gases is the silicon tetrafluoride that purity reaches 99.99%, impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 50

(1) catalyzer is CoF ₃, silicon-containing material is SiCl ₄, fluorine-containing material is ClF ₃, fluorine silicon is than being 0.025:1, and diluent media is air, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 61%, and productive rate is 20%.

(2) with embodiment 4 step (2);

Embodiment 51

(1) catalyzer is CeF ₃, silicon-containing material is SiCl ₄, fluorine-containing material is ClF, and fluorine silicon is than being 3:1, and diluent media is He, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 25%.

(2) with embodiment 3 step (2);

Embodiment 52

(1) do not use catalyzer, silicon-containing material is SiCl ₄, fluorine-containing material is NF ₃, fluorine silicon is than being 1:1, and temperature of reaction is 499 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 10 step (2);

Embodiment 53

(1) silicon-containing material is SiBr ₄, fluorine silicon is than being 22:1, and diluent media is SiF ₄, temperature of reaction is 999 DEG C, and all the other are with embodiment 1 step (1);

(2) with embodiment 11 step (2);

Embodiment 54

(1) do not use catalyzer, silicon-containing material is SiBr ₄, fluorine-containing material is COF ₂, reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 19%.

(2) with embodiment 12 step (2);

Embodiment 55

(1) catalyzer is CoF ₃, silicon-containing material is SiBr ₄, fluorine-containing material is ClF ₃, fluorine silicon is than being 3:1, and diluent media is N ₂, temperature of reaction is 1001 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 95%, and productive rate is 94%.

(2) with embodiment 3 step (2);

Embodiment 56

(1) catalyzer is CeF ₃, silicon-containing material is SiBr ₄, fluorine-containing material is ClF, and fluorine silicon is than being 1:1, and reaction pressure is 0.1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 65%, and productive rate is 18%.

(2) with embodiment 10 step (2);

Detect purified gases, known: purified gases is the silicon tetrafluoride that purity reaches 99.999%, productive rate is 18%; Impurity (SiF ₃) ₂o content < 0.1ppm, HF content < 0.1ppm, F ₂content < 0.1ppm.

Embodiment 57

(1) catalyzer is MnF ₂, silicon-containing material is SiBr ₄, fluorine-containing material is NF ₃, fluorine silicon is than being 30:1, and temperature of reaction is 1001 DEG C, and reaction pressure is 0.1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 9 step (2);

Embodiment 58

(1) silicon-containing material is SiI ₄, fluorine silicon is than being 1:1, and diluent media is N ₂, temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 1 step (2);

Embodiment 59

(1) do not use catalyzer, silicon-containing material is SiI ₄, fluorine-containing material is COF ₂, fluorine silicon is than being 0.025:1, and temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 99.5%, and productive rate is 99%.

(2) purifying reactive material is hydrofluoride CsHF ₂, crude product hydrofluosilicate is crude product CsHSiF ₆, hydrofluosilicate is CsHSiF ₆, heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 2 step (2);

Embodiment 60

(1) catalyzer is CoF ₃, silicon-containing material is SiI ₄, fluorine-containing material is ClF ₃, fluorine silicon is than being 0.2:1, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 99%, and productive rate is 88%.

(2) with embodiment 4 step (2);

Embodiment 61

(1) catalyzer is CeF ₃, silicon-containing material is SiI ₄, fluorine-containing material is ClF, and diluent media is air, and temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 7 step (2);

Embodiment 62

(1) catalyzer is MnF ₂, silicon-containing material is SiI ₄, fluorine-containing material is NF ₃, fluorine silicon is than being 0.02:1, and diluent media is He, and temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 96%, and productive rate is 90%.

(2) with embodiment 10 step (2);

Embodiment 63

(1) do not use catalyzer, silicon-containing material is Si ₃n ₄, fluorine silicon is than being 1:1, and temperature of reaction is 1499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 11 step (2);

Embodiment 64

(1) do not use catalyzer, silicon-containing material is Si ₃n ₄, fluorine-containing material is COF ₂, fluorine silicon is than being 2:1, and diluent media is SiF ₄, temperature of reaction is 1001 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 12 step (2);

Embodiment 65

(1) catalyzer is CoF ₃, silicon-containing material is Si ₃n ₄, fluorine-containing material is ClF ₃, fluorine silicon ratio is 0.1:1,

Temperature of reaction is 1001 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 3 step (2);

Embodiment 66

(1) catalyzer is CeF ₃, silicon-containing material is Si ₃n ₄, fluorine-containing material is ClF, and fluorine silicon is than being 3:1, and diluent media is N ₂, temperature of reaction is 999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 99.9%, and productive rate is 90%.

(2) with embodiment 10 step (2);

Embodiment 67

(1) do not use catalyzer, silicon-containing material is Si ₃n ₄, fluorine-containing material is NF ₃, fluorine silicon is than being 0.025:1, and temperature of reaction is 1001 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) purifying reactive material is fluorochemical MgF ₂, crude product silicofluoride is crude product MgSiF ₆, silicofluoride is MgSiF ₆, heat pre-treatment temperature is 51 DEG C, and heat pre-treatment pressure is-0.09MPa, and heat decomposition temperature is 51 DEG C, and thermolysis pressure is-0.09MPa, and all the other are with embodiment 1 step (2);

Embodiment 68

(1) silicon-containing material is SiC, and fluorine silicon is than being 0.25:1, and diluent media is N ₂, temperature of reaction is 51 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 18%.

(2) with embodiment 1 step (2);

Embodiment 69

(1) do not use catalyzer, silicon-containing material is SiC, and fluorine-containing material is COF ₂, fluorine silicon is than being 2:1, and temperature of reaction is 1001 DEG C, and reaction pressure is 0MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 21 step (2);

Embodiment 70

(1) catalyzer is CoF ₃, silicon-containing material is SiC, and fluorine-containing material is ClF ₃, fluorine silicon is than being 1:6, and diluent media is SiF ₄, temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 4 step (2);

Embodiment 71

(1) catalyzer is CeF ₃, silicon-containing material is SiC, and fluorine-containing material is ClF, and diluent media is air, and temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 9 step (2);

Embodiment 72

(1) catalyzer is MnF ₂, silicon-containing material is SiC, and fluorine-containing material is NF ₃, fluorine silicon is than being 1:1, and diluent media is He, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 93%, and productive rate is 88%.

(2) with embodiment 10 step (2);

Embodiment 73

(1) silicon-containing material is SiB ₆, diluent media is SiF ₄, temperature of reaction is 1 DEG C, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 14%.

(2) with embodiment 11 step (2);

Embodiment 74

(1) do not use catalyzer, silicon-containing material is SiB ₆, fluorine-containing material is COF ₂, fluorine silicon is than being 30:1, and temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 12 step (2);

Embodiment 75

(1) catalyzer is CoF ₃, silicon-containing material is SiB ₆, fluorine-containing material is ClF ₃, fluorine silicon is than being 2:1, and diluent media is SiF ₄, temperature of reaction is 499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 3 step (2);

Embodiment 76

(1) catalyzer is SnF ₂, silicon-containing material is SiB ₆, fluorine-containing material is ClF, and fluorine silicon is than being 20:1, and diluent media is SiF ₄, temperature of reaction is 480 DEG C, and reaction pressure is 0.4MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 10 step (2);

Embodiment 77

(1) catalyzer is MnF ₂, silicon-containing material is SiB ₆, fluorine-containing material is NF ₃, fluorine silicon ratio is 0.2:1,

Temperature of reaction is 100 DEG C, and reaction pressure is 0.2MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 60%, and productive rate is 50%.

(2) with embodiment 9 step (2);

Embodiment 78

(1) silicon-containing material is SiS ₂, fluorine silicon is than being 1:1, and diluent media is N ₂, temperature of reaction is 3999 DEG C, and reaction pressure is 5MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 97%, and productive rate is 90%.

(2) with embodiment 1 step (2);

Embodiment 79

(1) do not use catalyzer, silicon-containing material is SiS ₂, fluorine-containing material is COF ₂, fluorine silicon is than being 2:1, and temperature of reaction is-49 DEG C, and reaction pressure is-0.09MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 21 step (2);

Embodiment 80

(1) catalyzer is CoF ₃, silicon-containing material is SiS ₂, fluorine-containing material is ClF ₃, fluorine silicon is than being 0.025:1, and diluent media is SiF ₄, temperature of reaction is 999 DEG C, and reaction pressure is 1MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 4 step (2);

Embodiment 81

(1) catalyzer is CeF ₃, silicon-containing material is SiS ₂, fluorine-containing material is ClF, and fluorine silicon is than being 20:1, and diluent media is air, and temperature of reaction is 1 DEG C, and reaction pressure is 0.05MPa, and all the other are with embodiment 1 step (1);

Detect the gas prepared, knownly prepare gas is crude product silicon tetrafluoride to be purified, purity is 90%, and productive rate is 17%.

(2) with embodiment 3 step (2);

Embodiment 82

(1) catalyzer is MnF ₂, silicon-containing material is SiS ₂, fluorine-containing material is NF ₃, fluorine silicon is than being 15:1, and diluent media is He, and temperature of reaction is 1499 DEG C, and reaction pressure is 0.5MPa, and all the other are with embodiment 1 step (1);

(2) with embodiment 8 step (2);

Embodiment 1 ~ 82 is summed up as shown in table 1.

Table 1

Above, be used for illustrating in greater detail the present invention by partial, non-limiting specific embodiment, but the present invention is not limited to described embodiment, what describe in embodiment and specification sheets just illustrates principle of the present invention; That is; the above embodiment is only a part of preferred embodiment of the present invention; interest field of the present invention can not be limited with this; for those skilled in the art; under the prerequisite not departing from spirit of the present invention, principle and scope; the present invention also can make various change, improvements and modifications; these additional features improved can exist separately or with any combination, and these changes, improvements and modifications also should be considered as within claimed invention scope of the present invention.

Claims

1. a preparation method for silicon tetrafluoride, is characterized in that: described preparation method comprises:

Silicon-containing material is more than one in silicon, silane, silicon-dioxide, silica gel, metal silicide, trichlorosilane, dichloro hydrogen silicon, a chlorine hydrogen silicon, silicon tetrachloride, silicon bromide, iodate silicon, silicon nitride, silicon carbide, silicon boride and silicon sulfide;

Fluorine-containing material is more than one in nitrogen trifluoride, fluorine gas, carbonyl fluoride, chlorine trifluoride and chlorine monofluoride;

2. the preparation method of a kind of silicon tetrafluoride according to claim 1, is characterized in that: the fluorine atom in fluorine-containing material is 0.025 ~ 40:1 with the ratio of the amount of substance of the Siliciumatom in silicon-containing material.

3. the preparation method of a kind of silicon tetrafluoride according to claim 1 and 2, is characterized in that: reaction pressure is ﹣ 0.05MPa ~ 1MPa or 0.05MPa ~ 0.5MPa.

4. the preparation method of a kind of silicon tetrafluoride stated according to claim 3, is characterized in that: for different silicon-containing materials and fluorine-containing material:

(1), when silicon-containing material is silicon-dioxide, when fluorine-containing material is nitrogen trifluoride, temperature of reaction is 701 DEG C ~ 3499 DEG C;

(2), when silicon-containing material is silicon-dioxide, when fluorine-containing material is fluorine gas, temperature of reaction is 2051 DEG C ~ 3499 DEG C;

(3), except (1) and (2), when other silicon-containing material and fluorine-containing material, temperature of reaction is 1 DEG C ~ 1499 DEG C.

5. the preparation method of a kind of silicon tetrafluoride stated according to claim 3, is characterized in that: for different silicon-containing materials and fluorine-containing material:

(1), when silicon-containing material is silicon-dioxide, when fluorine-containing material is nitrogen trifluoride, temperature of reaction is 851 DEG C ~ 2999 DEG C;

(2), when silicon-containing material is silicon-dioxide, when fluorine-containing material is fluorine gas, temperature of reaction is 2101 DEG C ~ 2999 DEG C;

(3), except (1) and (2), when other silicon-containing material and fluorine-containing material, temperature of reaction is 1 DEG C ~ 999 DEG C.

6. the preparation method of a kind of silicon tetrafluoride stated according to claim 3, is characterized in that: for different silicon-containing materials and fluorine-containing material:

(1), when silicon-containing material is silicon-dioxide, when fluorine-containing material is nitrogen trifluoride, temperature of reaction is 1001 DEG C ~ 2699 DEG C;

(2), when silicon-containing material is silicon-dioxide, when fluorine-containing material is fluorine gas, temperature of reaction is 2501 DEG C ~ 2699 DEG C;

(3), except (1) and (2), when other silicon-containing material and fluorine-containing material, temperature of reaction is 51 DEG C ~ 499 DEG C.

7. the preparation method of a kind of silicon tetrafluoride according to claim 1 and 2, it is characterized in that: use interpolation diluent media to dilute, diluent media is at least one in nitrogen, air, helium and silicon tetrafluoride, is silicon-containing material and/or fluorine-containing material by diluent materials; Diluent media adds before silicon-containing material and fluorine-containing material mixing, dilutes at least one party in silicon-containing material or fluorine-containing material, or adds after silicon-containing material and fluorine-containing material mixing;

And/or use catalyzer, catalyzer is at least one in the metal fluoride of the metal fluoride of silver, the metal fluoride of cobalt, the metal fluoride of manganese, the metal fluoride of tin and cerium.

8. a purification process for silicon tetrafluoride, is characterized in that: described method comprises:

Crude product silicon tetrafluoride to be purified and purifying reactive material are reacted and prepares crude product M _m(SiF ₆) _por crude product M _n(HSiF ₆) _q, by crude product M _m(SiF ₆) _por crude product M _n(HSiF ₆) _qcarry out thermolysis, obtain the silicon tetrafluoride of purifying;

Crude product silicon tetrafluoride to be purified adopts existing silicon tetrafluoride preparation method or adopts the preparation method of a kind of silicon tetrafluoride as claimed in claim 1 to prepare;

Purifying reactive material is MF _x, M (HF ₂) _y, HF and NH ₃in at least one, when purifying reactive material is HF, MF should be contained at least simultaneously _x; When purifying reactive material is NH ₃time, should contain HF, described M is metal or NH at least simultaneously ₄, F is fluorine atom, HF ₂for hydrogen fluorine root, x is the number of F, and 1≤x, y are HF ₂number, 1≤y, SiF ₆for silicofluoric acid root, HSiF ₆for hydrofluosillicic acid root, m is M _m(SiF ₆) _pthe number of middle M, 1≤m, n are M _n(HSiF ₆) _qthe number of middle M, 1≤n, p are SiF ₆number, 1≤p, q are HSiF ₆number, 1≤q.

9. the purification process of a kind of silicon tetrafluoride according to claim 8, is characterized in that: crude product M _m(SiF ₆) _pfor (NH ₄) ₂siF ₆, FeSiF ₆, CuSiF ₆, CoSiF ₆or CrSiF ₆; Crude product M _n(HSiF ₆) _qfor NH ₄hSiF ₆, LiHSiF ₆, NaHSiF ₆, KHSiF ₆or CsHSiF ₆.

10. the purification process of a kind of silicon tetrafluoride according to claim 8 or claim 9, it is characterized in that: the temperature that crude product silicon tetrafluoride to be purified and purifying reactive material are reacted is-99 DEG C ~ 999 DEG C, reaction pressure is ﹣ 0.09MPa ~ 2MPa.

The purification process of 11. a kind of silicon tetrafluorides according to claim 8 or claim 9, is characterized in that: by crude product M _m(SiF ₆) _por crude product M _n(HSiF ₆) _qthe heat decomposition temperature carrying out thermolysis is 51 DEG C ~ 1999 DEG C, 201 DEG C ~ 999 DEG C or 301 DEG C ~ 499 DEG C; Thermolysis pressure is ﹣ 0.09MPa ~ 5MPa or 0.05MPa ~ 0.5MPa.

The purification process of 12. a kind of silicon tetrafluorides according to claim 8 or claim 9, is characterized in that: to crude product M before thermolysis _m(SiF ₆) _por crude product M _n(HSiF ₆) _qmore than one methods in following (1), (2) and (3) are adopted to process:

(1) dissolution filter, recrystallization, drying and/or vacuumize and carry out purifying;

(2) heat pre-treatment, heat pre-treatment temperature is 51 DEG C ~ 1999 DEG C, and heat pre-treatment pressure is-0.09MPa ~ 0.5MPa;

(3) pressure≤-0.099MPa is evacuated to.