CN104724711A - Manufacturing method for silane type product - Google Patents
Manufacturing method for silane type product Download PDFInfo
- Publication number
- CN104724711A CN104724711A CN201510056469.1A CN201510056469A CN104724711A CN 104724711 A CN104724711 A CN 104724711A CN 201510056469 A CN201510056469 A CN 201510056469A CN 104724711 A CN104724711 A CN 104724711A
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- Prior art keywords
- silicon
- chloride
- magnesium
- silicomethane
- ammonia
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Abstract
The invention provides a manufacturing method for a silane type product. The manufacturing method for the silane type product comprises the following steps: A, preparing magnesium silicide from silica powder and magnesium powder in the presence of a catalyst; B, enabling the magnesium silicide and ammonia chloride to react to generate silane type gas and hexammoniated magnesium chloride in the presence of liquid ammonia and the catalyst; C, performing a separation reaction on the hexammoniated magnesium chloride to obtain magnesium chloride and liquid ammonia; D, performing electrolysis on the magnesium chloride to obtain magnesium powder and chlorine gas; E, performing a reaction on the chlorine gas obtained in the step D and the liquid ammonia obtained in the step C to generate ammonia chloride, and applying the obtained ammonia chloride to the step B. The manufacturing method for the silane type product is completely completed under a chloride-free and halogen-free environment; the risk of chloride and halogen in the subsequent use can be fully eliminated; furthermore, all side-products and intermediate products can be recovered and reutilized, so that the top requirement of environment protection is achieved.
Description
Technical field
The invention belongs to silicane product manufacturing technical field, espespecially a kind of processing procedure comprehensively reclaims the silicane Manufacturing Method of Products that byproduct re-uses entirely.
Background technology
In microelectronic product manufacturing processed, silicon is in order to conductive layer each in insulating electron precision components.Due to assembly, such as chip, pursues precision again and again, specifications design is more and more thinner, from micron order progress to nano level, so insulate on Si layer mechanically cannot cut formation, and must be formed by gas phase lamination method, so the use of silicane forms necessary material.
Traditional silicomethane preparation method has two kinds at least.One is silicon magnesium processes, or claims little Song method, with silica flour and magnesium powder for original material, and first synthesizing magnesium silicide, Si+2Mg----→ Mg
2si.React according to usage ratio with magnesium silicide and ammonia chloride, under the environment of liquefied ammonia, generate silicomethane gas phase and magnesium chloride hex-ammoniate solid phase residue, reaction formula is again:
Clearly, this method can obtain silicomethane for.And magnesium chloride hex-ammoniate is a solid phase article, so chlorine element can not exist in the special gas of the silicomethane of gas phase.But magnesium chloride hex-ammoniate is a kind of solid waste, if carry out waste disposal, for environmental protection, aobvious have improper.Moreover this classical production process only can generate silicomethane, cannot generate as related productss such as silicon ethane, silicon propane.
Second method is with Trichlorosilane purification method (being namely commonly called as UCC method).The processing procedure of this method, first reacts with silica flour and hydrogenchloride (being commonly called as hydrochloric acid) and generates trichlorosilane, Si+3HCl----------→ HSiCl
3+ H
2.Again with trichlorosilane and hydrogen reaction, form dichloro hydrogen silicon and hydrogenchloride by hydrogen is combined with chlorine element, HSiCl
3+ H
2---→ H
2siCl
2+ HCl.Sequentially again with dichloro hydrogen silicon and hydrogen reaction, form monochloro hydrogen silicon and hydrogenchloride by hydrogen is combined with chlorine element, H
2siCl
2+ H
2---→ H
3siCl+HCl.Then, monochloro hydrogen silicon again with hydrogen reaction, be namely combined with chlorine element by hydrogen and form silicomethane and hydrogenchloride, H
3siCl+H
2-----→ SiH
4+ HCl.
This method can generate silicomethane.But the product of silicon ethane, silicon propane etc. then cannot be obtained by present method.And this method needs hydrochloric acid and reacts wherein always, danger and the corrodibility of obvious processing procedure all significantly improve.Separately, in this method, each reactant and resultant all with gas-phase reaction output, so be separated take out silicomethane time, be usually easier to there is chlorine element in silicomethane gases.As everyone knows, in electronic package, be afraid of to there is chlorine element most, even if amount is very small, still there is very large risk in the corrodibility for precise electronic assembly.So, when the progress of high-tech electronic product is to nano level, use the material with chlorine element risk not to be allowed to.When especially forming insulate on Si layer in electronic package, because formation time is short, form isolated film layer thinner, formation temperature needs to reduce, and the flatness requirement on film top layer is higher.These requirements, the characteristic of silicomethane is not enough to some extent and be difficult to be used, only have silicon ethane even silicon propane could meet the sustainable development requirement of these high-tech electronic products.
In other words; the no matter industry such as semi-conductor, access memory, liquid crystal display, solar cell, energy-saving glass; gradually turn to silicon ethane from the use of silicomethane; and be proprietary common recognition for the requirement of environment protection; therefore, the manufacture method that a kind of novelty effectively meets the demand must be arisen at the historic moment.
Summary of the invention
In order to solve the problem, the present invention is achieved through the following technical solutions.
A manufacture method for silicane product, comprises following steps:
A, generate magnesium silicide in the presence of a catalyst with silica flour and magnesium powder,
B, react with magnesium silicide and ammonia chloride, under liquefied ammonia and catalyzer exist, generate silane based gas and magnesium chloride hex-ammoniate, reaction formula is:
Wherein m=2n+2
C, magnesium chloride hex-ammoniate is obtained magnesium chloride and liquefied ammonia by separating reaction;
MgCl
2·6NH
3----------→MgCl
2+6NH
3
D, magnesium chloride is generated magnesium powder and chlorine through electrolysis;
MgCl
2--------→Mg+Cl
2
E, the liquefied ammonia of the chlorine of step D and step C reacted generate ammonia chloride, the ammonia chloride obtained is used for using in step B,
Cl
2+H
2------→2HCl
NH
3+HCl-------→NH
4Cl。
Further, the catalyzer of described step B is for being selected from one of aluminium salt, zinc salt, lawrencium salt, precious metal salt or its multiple mixture.
Further, described precious metal salt is platinum salt.
Further, the silane based gas obtained by step B cools to-60 DEG C to-120 DEG C, isolates silicon propane; Cool to-120 DEG C to-170 DEG C again, isolate silicon ethane: and then cool to-170 DEG C to-240 DEG C, isolate silicomethane.
Further, silicomethane is warming up to more than-170 DEG C, makes silicomethane become gas phase from liquid phase, and then lower the temperature, in-180 DEG C to-220 DEG C temperature, obtain high purity silicon methane; Silicon ethane is warming up to more than-120 DEG C, makes silicon ethane become gas phase from liquid phase, and then lower the temperature, in-130 DEG C to-160 DEG C temperature, obtain high purity silicon ethane; Silicon propane is warming up to more than-60 DEG C, makes silicon propane become gas phase from liquid phase, and then lower the temperature, in-70 DEG C to-110 DEG C temperature, obtain high purity silicon propane.
Further, silicomethane, silicon ethane, silicon propane are carried out purifying by molecular sieve.
Further, the ammonia that obtains of step C is for using in step B.
Further, the magnesium powder that obtains of step D is for using in steps A
The inventive method institute's by-product and intermediates all can reclaim and re-use, to reach the peak demand of environment protection.
The inventive method not only can generate silicomethane, can also generate silicon ethane and silicon bromopropane product.
The inventive method completes completely under the environment without chlorine and halogen, can exempt the risk for chlorine and halogen in follow-up use completely.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail
A manufacture method for silicane product, comprises the following step:
A, first under the environment of catalyzer, generate magnesium silicide with silica flour and magnesium powder,
B, react with magnesium silicide and ammonia chloride, under the environment of liquefied ammonia and catalyzer, generate silicane and magnesium chloride hex-ammoniate, reaction formula is:
Wherein m=2n+2
C, magnesium chloride hex-ammoniate are a solids product, then obtain magnesium chloride and liquefied ammonia through separating reaction in addition, and liquefied ammonia can drop in above-mentioned processing procedure B and following processing procedure E again and use:
MgCl
2·6NH
3----------→MgCl
2+6NH
3
D, magnesium chloride also generate magnesium powder and chlorine again through electrolysis, magnesium powder is solid phase, can drop in the A in above-mentioned processing procedure and use:
E, chlorine generate ammonia chloride with liquefied ammonia building-up reactions again, and the B that ammonia chloride is dropped in above-mentioned processing procedure uses, and wherein liquefied ammonia comes from the C in above-mentioned processing procedure, and in other words, the ammonia of processing procedure C generation can be used for processing procedure B and E to use:
Cl
2+H
2-------→2HCl
NH
3+HCl------→NH
4CL
Can find out the product generating silicane in rapid B from above-mentioned reaction formula, due to gases such as silicomethane, silicon ethane, silicon propane, although be all gas, molecular weight is had nothing in common with each other, and causes the temperature required difference that liquefies/gasify.Use its physical property different, the products such as silicomethane, silicon ethane, silicon propane can be obtained respectively through being separated, independently being answered different user demand in existence side to allow variant paraffinic product.
Why the present invention can obtain paraffinic product after manufacture reaction, and is not only silicomethane, and mainly apply catalyzer in the reaction, catalyzer is mainly metal-salt, such as, and aluminium salt, zinc salt, lawrencium salt, precious metal salt etc.Precious metal salt can be platinum salt etc.It is used in combination that catalyzer can be selected from one or more of above-mentioned various metal-salt.
Above-mentioned silicane product is a mixed gas.Silicane mixed gas is isolated the method for silicomethane, silicon ethane, silicon propane etc., first silicane mixed gas can be cooled to liquid phase, progressively heat up again, sequentially collect the silicomethane, silicon ethane, silicon propane etc. of gas phase, and reach the object isolating single silicane product.Identical, can be lowered the temperature from the silicane mixed gas of gas phase, sequentially make silicon propane, silicon ethane, silicomethane liquefy and reach the object isolating single silicane product.
For making silicomethane, silicon ethane and silicon propane high degree of accuracy purifying, silicomethane, silicon ethane, silicon propane can be given purifying with temperature head again.The purifying of silicomethane, silicon ethane and silicon propane also can use molecular sieve to give purifying.Certainly, for obtaining the object of more high degree of accuracy purifying, temperature head, molecular sieve not only can be used alone, and can also the two combinationally use.Purification process as other equivalences can be used.
Embodiment 1
Steps A, B, C, D, E is carried out according to aforesaid method.Wherein, the catalyzer that step B uses is zinc salt and a lawrencium salt mixture; The separation of step C sequentially isolates silicon propane, silicon ethane, silicomethane by cooling.First silicane mixed gas is cooled to-120 DEG C, isolates silicon propane; Be cooled to-170 DEG C again, isolate silicon ethane: and then be cooled to-240 DEG C, isolate silicomethane.Therefore, silicomethane, silicon ethane and silicon propane all present with liquid phase.
After various silicane product output, need through the operation of precision purifying, to meet the high-accuracy purity of high-tech electronic product, in detached job, again silicomethane is warming up to more than-170 DEG C, silicomethane is made to become gas phase from liquid phase, and then lower the temperature, in the temperature of-220 DEG C, obtain silicomethane, therefore, non-the impure of genus Ben Wendu will be removed, and purity is promoted.Identical, silicon ethane is warming up to more than-120 DEG C, makes silicon ethane become gas phase from liquid phase, and then lower the temperature, obtain silicon ethane in the temperature of-160 DEG C, therefore, non-the impure of genus Ben Wendu will be removed, and purity is promoted.In like manner, silicon propane is warming up to more than-60 DEG C, makes silicon propane become gas phase from liquid phase, and then lower the temperature, obtain silicon propane in the temperature of-110 DEG C, therefore, non-the impure of genus Ben Wendu will be removed, and purity is promoted.
Embodiment 2
Repeat embodiment 1, difference is, the catalyzer that step B uses is zinc salt; In step C, silicane mixed gas is cooled to-60 DEG C, isolates silicon propane; Cool to-120 DEG C again, isolate silicon ethane: and then cool to-170 DEG C, isolate silicomethane.In purifying operation, silicomethane is cooled to-180 DEG C again, and silicon ethane is cooled to-130 DEG C again, and silicon propane is cooled to-70 DEG C again.
Embodiment 3
Repeat embodiment 1, difference is, the catalyzer that step B uses is platinum salt; In step C, silicane mixed gas is cooled to-90 DEG C, isolates silicon propane; Cool to-145 DEG C again, isolate silicon ethane: and then cool to-205 DEG C, isolate silicomethane.In purifying operation, silicomethane is cooled to-200 DEG C again, and silicon ethane is cooled to-145 DEG C again, and silicon propane is cooled to-90 DEG C again.
Embodiment 4
Repeat embodiment 1, difference is, the catalyzer that step B uses is aluminium salt; In step C, silicane mixed gas is cooled to-100 DEG C, isolates silicon propane; Cool to-130 DEG C again, isolate silicon ethane: and then cool to-215 DEG C, isolate silicomethane.In purifying operation, silicomethane is cooled to-190 DEG C again, and silicon ethane is cooled to-150 DEG C again, and silicon propane is cooled to-100 DEG C again.
Embodiment 5
Repeat embodiment 3, difference is, the catalyzer that step B uses is aluminium salt, zinc salt and lawrencium salt; In step C, silicane mixed gas is cooled to-70 DEG C, isolates silicon propane; Cool to-150 DEG C again, isolate silicon ethane: and then cool to-220 DEG C, isolate silicomethane.In purifying operation, silicomethane is cooled to-210 DEG C again, and silicon ethane is cooled to-150 DEG C again, and silicon propane is cooled to-80 DEG C again.
Embodiment 6
Repeat embodiment 1, difference is, the catalyzer that step B uses is aluminium salt, platinum salt, zinc salt and lawrencium salt; In step C, silicane mixed gas is cooled to-90 DEG C, isolates silicon propane; Cool to-145 DEG C again, isolate silicon ethane: and then cool to-205 DEG C, isolate silicomethane.In purifying operation, silicomethane is cooled to-200 DEG C again, and silicon ethane is cooled to-135 DEG C again, and silicon propane is cooled to-90 DEG C again.
Because single silane product is separated by the present invention, so the operation of high degree of accuracy purifying is easier than the operation of mixed species gas precision purifying, also follow-up manufacture method is simplified, and after high precision purifying, high purity 99.999% can be obtained, the even product of more than 99.9999%, thus meet high-tech electronic product during fabrication for the demand of silicane raw material.
Above detailed description is in order to disclose technology contents and the feature of the present invention, and be aided with embodiment explanation, those skilled in the art are implemented accordingly, but the interest field of above-mentioned explanation not for limiting the present invention, such as simple displacement or the replacement of equivalence techniques, must be subordinate to the category of the present invention.
Claims (8)
1. a manufacture method for silicane product, comprises following steps:
A, generate magnesium silicide in the presence of a catalyst with silica flour and magnesium powder;
Si+2Mg------→Mg
2Si
Catalyzer
B, react with magnesium silicide and ammonia chloride, under liquefied ammonia and catalyzer exist, generate silane based gas and magnesium chloride hex-ammoniate, reaction formula is:
NH
3
Mg2Si+NH4Cl----------------→Si
nH
m+MgCl
2·6NH
3
Catalyzer
Wherein m=2n+2
C, magnesium chloride hex-ammoniate is obtained magnesium chloride and liquefied ammonia by separating reaction;
MgCl
2·6NH
3----------→MgCl
2+6NH
3
D, magnesium chloride is generated magnesium powder and chlorine through electrolysis;
MgCl
2--------→Mg+Cl
2
E, the liquefied ammonia of the chlorine of step D and step C reacted generate ammonia chloride, the ammonia chloride obtained is used for using in step B,
Cl
2+H
2--------→2HCl
NH
3+HCl-------→NH
4Cl。
2. method according to claim 1, is characterized in that, the catalyzer of described step B is for being selected from one of aluminium salt, zinc salt, lawrencium salt, precious metal salt or its multiple mixture.
3. method according to claim 1, is characterized in that, described precious metal salt is platinum salt.
4. method according to claim 1, is characterized in that, the silane based gas obtained by step B cools to-60 DEG C to-120 DEG C, isolates silicon propane; Cool to-120 DEG C to-170 DEG C again, isolate silicon ethane: and then cool to-170 DEG C to-240 DEG C, isolate silicomethane.
5. method according to claim 4, is characterized in that, silicomethane is warming up to more than-170 DEG C, makes silicomethane become gas phase from liquid phase, and then lowers the temperature, and obtains high purity silicon methane in-180 DEG C to-220 DEG C temperature; Silicon ethane is warming up to more than-120 DEG C, makes silicon ethane become gas phase from liquid phase, and then lower the temperature, in-130 DEG C to-160 DEG C temperature, obtain high purity silicon ethane; Silicon propane is warming up to more than-60 DEG C, makes silicon propane become gas phase from liquid phase, and then lower the temperature, in-70 DEG C to-110 DEG C temperature, obtain high purity silicon propane.
6. the method according to claim 4 or 5, is characterized in that, silicomethane, silicon ethane, silicon propane are carried out purifying by molecular sieve.
7. method according to claim 1, is characterized in that, the liquefied ammonia that step C obtains is for using in step B.
8. method according to claim 1, is characterized in that, the magnesium powder that step D obtains is for using in steps A.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672979A (en) * | 2015-11-06 | 2017-05-17 | 岳阳高圭新材料有限公司 | Device and method for continuously preparing silicane and disilane through magnesium silicide method |
| CN106672978A (en) * | 2015-11-06 | 2017-05-17 | 岳阳高圭新材料有限公司 | Technology for continuously carrying out closed-loop production on silane and polycrystalline silicon through magnesium silicide combination method |
| WO2017193881A1 (en) * | 2016-05-09 | 2017-11-16 | 浙江迅鼎半导体材料科技有限公司 | Method for manufacturing disilane |
| CN109626379A (en) * | 2017-10-09 | 2019-04-16 | 烟台万华电子材料有限公司 | Alloying compound reacts the method and apparatus of production silanes product with ammonium chloride in liquefied ammonia |
| CN112661161A (en) * | 2020-12-28 | 2021-04-16 | 烟台万华电子材料有限公司 | Method for continuously producing high-order silane |
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| CN101298336A (en) * | 2008-06-06 | 2008-11-05 | 浙江理工大学 | Synthetic method of magnesium chloride hexammoniate |
| CN101327930A (en) * | 2008-07-18 | 2008-12-24 | 浙江理工大学 | Use of anhydrous magnesium chloride in silane purification |
| CN102515169A (en) * | 2011-12-16 | 2012-06-27 | 天津市泰亨气体有限公司 | Method for producing disilane by reaction of magnesium silicide and ammonium chloride |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298336A (en) * | 2008-06-06 | 2008-11-05 | 浙江理工大学 | Synthetic method of magnesium chloride hexammoniate |
| CN101327930A (en) * | 2008-07-18 | 2008-12-24 | 浙江理工大学 | Use of anhydrous magnesium chloride in silane purification |
| CN102515169A (en) * | 2011-12-16 | 2012-06-27 | 天津市泰亨气体有限公司 | Method for producing disilane by reaction of magnesium silicide and ammonium chloride |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672979A (en) * | 2015-11-06 | 2017-05-17 | 岳阳高圭新材料有限公司 | Device and method for continuously preparing silicane and disilane through magnesium silicide method |
| CN106672978A (en) * | 2015-11-06 | 2017-05-17 | 岳阳高圭新材料有限公司 | Technology for continuously carrying out closed-loop production on silane and polycrystalline silicon through magnesium silicide combination method |
| CN106672979B (en) * | 2015-11-06 | 2019-06-25 | 岳阳高圭新材料有限公司 | A kind of device and method that magnesium silicide method continuously prepares monosilane and disilane |
| CN106672978B (en) * | 2015-11-06 | 2019-07-09 | 岳阳高圭新材料有限公司 | The technique of magnesium silicide combination method continuous closed-loop production silane and polysilicon |
| WO2017193881A1 (en) * | 2016-05-09 | 2017-11-16 | 浙江迅鼎半导体材料科技有限公司 | Method for manufacturing disilane |
| CN109626379A (en) * | 2017-10-09 | 2019-04-16 | 烟台万华电子材料有限公司 | Alloying compound reacts the method and apparatus of production silanes product with ammonium chloride in liquefied ammonia |
| CN112661161A (en) * | 2020-12-28 | 2021-04-16 | 烟台万华电子材料有限公司 | Method for continuously producing high-order silane |
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