CN103359738A - Method for removing impurities in silane and equipment for method - Google Patents
Method for removing impurities in silane and equipment for method Download PDFInfo
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- CN103359738A CN103359738A CN2012100860155A CN201210086015A CN103359738A CN 103359738 A CN103359738 A CN 103359738A CN 2012100860155 A CN2012100860155 A CN 2012100860155A CN 201210086015 A CN201210086015 A CN 201210086015A CN 103359738 A CN103359738 A CN 103359738A
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Abstract
The invention provides a method for removing impurities in silane. The method comprises the following steps of: introducing silane into a thermal decomposition tube for performing thermal decomposition, and removing solid impurities, wherein the thermal decomposition temperature is 200-500DEG C, the length of the thermal decomposition tube is 0.5-3m, and the flow of the silane is 0.1-5L/min. The invention also provides equipment for removing the impurities in the silane. The method provided by the invention is obvious in impurity removal effect, and energy is saved.
Description
Technical field
The invention belongs to the purification field of silane, the removal method that relates in particular to impurity in the silane reaches the equipment that is used for the method.
Background technology
A kind of removal method of microimpurity in silane, relate generally to (the minor component such as Si2H60 of diborane (B2H6), phosphine (PH3), arsine (AsH3) and silicoethane, B2H6, PH3, AsH3 and Si2H6 are owing to chemical property and silane is close and content is lower, also remarkable to the silane property effect, so the purification that B2H6, PH3, AsH3 and Si2H6 must remove silane seems particularly important.
The technique of the main employing of industrial refining silane has absorption method, rectification method and their combination.
CN201010148476 discloses the refining method of purifying of electronic-grade silane in a kind of polycrystalline production process, comprise the steps: 1) thick silane is passed into lightness-removing column, working pressure 1.8～the 2.5MPa of tower, nitrogen, methane, hydrogen are removed at cat head in head temperature-120～-80 ℃; 2) thick silane goes out to enter the first weight-removing column from tower bottom flow, the working pressure 1.8～2.5MPa of tower, and ethane, boron, phosphorus etc. are removed in head temperature-70～-40 ℃ at the bottom of tower; The silane of 3) discharging from cat head enters the adsorption tower of series connection, and the working pressure of tower is 1.6～2.3MPa, removes ethene; 4) silane enters the second weight-removing column, the working pressure 1.6～2.3MPa of tower, and head temperature-70～40 ℃ is removed ethyl silicane.The present invention drops to below 1.5 * 10-9 the content of nitrogen, methane, hydrogen in the refining rear silane of purifying; The content of ethane, ethylsilane, diethylsilane, ethene, ethyl silicane, boron, phosphorus drops to below 3.5 * 10-9, finally the purity of thick silane can be purified to more than 99.9999999%, satisfies the service requirements of electronics and semicon industry.
CN200910109206 discloses a kind of removal method of microimpurity in silane, comprises the employing large pores cation exchange resin, and described large pores cation exchange resin is carried out modification; Large pores cation exchange resin after the modification is packed in the adsorption tower, after purging deoxygenation, silane gas is passed through.Microimpurity in silane removal method provided by the invention has been removed the minor components such as the B2H6 in the silane, PH3, AsH3 and Si2H6 significantly, and each component concentration is down to below 0.5 * 10-9, reaches electronics and semicon industry to the service requirements of high purity silane.
CN201020134192 the utility model discloses a kind of molecular sieve purification device of silane preparation, mainly presses the valve of its system function by connecting in the middle of it by pure silane outlet, strainer, the outlet of pure tail gas, coiled pipe post, thief hole, U tubing string, 4A molecular sieve adsorption post, 5A molecular sieve adsorption post, thick silane admission port, under meter, vacuum pump interface, emptying water seal tank, oil sealing.Manometric connection line is assembled into one and consists of.This device is reasonable in design, makes simply, and provides desirable instrument for silane improves purity.
There are following several large shortcomings in above-mentioned prior art: (1) silane low temperature fractionation removal of impurities purification energy consumption is large, condensing temperature is-112 ℃ under the normal pressure of silane gas, need to consume a large amount of energy during low temperature fractionation, remove trace impurity in the silane make its reach the ppb rank or lower rectifying tower is required very high, it is inflammable and explosive that the complicated simultaneously silane of low-temperature distillation process is met air, high to the production safety requirement of low temperature fractionation; (2) the Adsorption impurity shortcoming such as the large pores cation exchange resin by modification, molecular sieve, gac is that dust removal rate is low, just must carry out repeatedly removal of impurities if obtain high purity silane, large pores cation exchange resin, molecular sieve, gac itself are easily brought new impurity into.
Summary of the invention
The present invention is for solving the technical problem that existing silane impurity-removing method energy consumption is large, dust removal rate low and easily bring new impurity into, provides that a kind of energy consumption is little, dust removal rate is high and do not introduce the silane impurity-removing method of new impurity and be used for the equipment of this impurity-removing method.
The invention provides the removal method of impurity in a kind of silane, the method carries out in the thermolysis pipe removing solid impurity after the thermolysis for silane is passed into; The temperature of described thermolysis is 200-500 ℃, and the length of described thermolysis pipe is 0.5-3m, and the flow of silane is 0.1-5L/min.
The present invention also provides a kind of equipment for method of the present invention, and this equipment comprises thermolysis pipe and the dust collection that is communicated with thermolysis Guan Yiduan.The silane gas that contains impurity enters the thermolysis pipe from the other end of thermolysis pipe and processes.
The present invention adopts thermolysis to remove phosphine, borine, arsine, silicoethane etc. to decompose temperature to be lower than the impurity technique of silane simple, compare the low temperature fractionation less energy consumption, and it is high that assorted efficient is removed in thermolysis, do not use sorbent material, can not bring new impurity into.
Description of drawings
Fig. 1 is the schematic diagram of equipment of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides the removal method of impurity in a kind of silane, the method carries out in the thermolysis pipe removing solid impurity after the thermolysis for silane is passed into; The temperature of described thermolysis is 200-500 ℃, and the length of described thermolysis pipe is 0.5-3m, and the flow of silane is 0.1-5L/min.
Stable under the SiH4 normal temperature, begin to decompose at 400 ℃, when being higher than 500 ℃, temperature is decomposed into silicon and hydrogen, and decompose in the time of 600 ℃ and accelerate, resolve into silicon and hydrogen in the time of 1000 ℃ fully.Phosphine is at room temperature stable, approximately 375 ℃ begin to decompose, approximately 600 ℃ decompose fully.Diborane can slowly decompose in room temperature, and temperature is more high more unstable, decomposes and accelerates, and resolves into hydrogen and boron during to 500 ℃ fully.Arsine is at room temperature stable, begins to decompose under 230-240 ℃.Silicoethane is more unstable than silane, slowly decomposes at normal temperatures to generate silane and hydrogen, decomposes at 300 ~ 500 ℃ to generate silane and hydrogen.
According to the removal method of impurity in the silane provided by the present invention, for conserve energy, preferably, in preheater, silane is being carried out preheating before the thermolysis.
According to the removal method of impurity in the silane provided by the present invention, in order better to remove the impurity in the silane, preferably, the silane of removing solid impurity is filtered.
According to the removal method of impurity in the silane provided by the present invention, in order not introduce new impurity, preferably, before silane is processed, remove the air in the whole equipment.
According to the removal method of impurity in the silane provided by the present invention, in order not introduce new impurity, more preferably, remove the method for the air in the whole equipment in this equipment, passing into nitrogen first, then vacuumize; The described flow that passes into nitrogen is 1-5L/min, and the time is 1-3 hour, and the described rear system absolute pressure that vacuumizes is 1-10Pa.
The present invention also provides a kind of equipment for method of the present invention, and this equipment comprises thermolysis pipe and the dust collection that is communicated with thermolysis Guan Yiduan.
According to equipment provided by the present invention, preferably, described equipment also comprises be used to the reaction vessel that holds high temperature heat conductive oil, agitator and Temperature controlled heater; Described agitator is positioned at reaction vessel and high temperature heat conductive oil is stirred, described Temperature controlled heater is positioned at reaction vessel and high temperature heat conductive oil is carried out temperature control, described thermolysis pipe is arranged in high temperature heat conductive oil, and described dust collection is positioned at the outside of reaction vessel.
According to equipment provided by the present invention, preferably, described equipment also comprises preheater, and described preheater is communicated with the other end of thermolysis pipe.
According to equipment provided by the present invention, preferably, described equipment also comprises the under meter that places before the preheater.
According to equipment provided by the present invention, preferably, described equipment also is provided with strainer after dust collection, and described strainer is communicated with dust collection.
Below in conjunction with Fig. 1 equipment of the present invention is further elaborated.
As shown in Figure 1, the used equipment of the removal of impurity in the silane of the present invention comprises thermolysis pipe 3 and the dust collection 7 that is communicated with thermolysis Guan Yiduan.Described equipment also comprises high temperature heat conductive oil 6, agitator 4 and Temperature controlled heater 5; Described agitator stirs high temperature heat conductive oil, and described Temperature controlled heater carries out temperature control to high temperature heat conductive oil, and described thermolysis pipe is arranged in high temperature heat conductive oil.Described equipment also comprises preheater 2, and described preheater is communicated with the other end of thermolysis pipe.Described equipment also comprises the under meter 1 that places before the preheater.Described equipment also is provided with strainer 8 after dust collection, described strainer is communicated with dust collection.Described equipment also comprises the K1 reducing valve, and the silane before the removal of impurities is by this valve access arrangement; K2, K3, K5 represent common high-cleanness valve, and K2 passes into nitrogen, and K3 connects vaccum-pumping equipment, and K5 surveys with gas chromatograph and is connected, and K4 represents back pressure valve, is connected with the silane collection device.
The working process of this equipment is: at first open agitator and Temperature controlled heater, make the temperature of thermal oil rise to set(ting)value, opened valve k2 high pure nitrogen purging system 1 hour, drive air in the system away, then close K1.Open the K3 valve and take intrasystem nitrogen away with vacuum pump, make system reach certain vacuum tightness, then close K3.Open pressurizing valve K1, back pressure valve K4 is set as the processing requirement value, the silane gas for the treatment of removal of impurities enters pipeline from valve K1, the flow of adjust flux meter, in the silane preheater, enter the thermolysis pipe after the preheating, heat decomposition temperature is lower than the phosphine of silane, borine, arsine, silicoethane etc. impurity decomposes in the thermolysis pipe, then the silane gas of high temperature enters the silane gas preheater, for the silane preheating provides heat, silane after impurity decomposes enters dust collection, the solid particulate that forms in the decomposition course inside deposits, cooled silane enters into the silane gathering system by strainer, behind system run all right, open K5 and the silane gas after purifying is sent into gas chromatograph test its purity, in order to monitor at any time the purity of the silane after the removal of impurities.
Also the present invention is described in further detail by reference to the accompanying drawings below by specific embodiment.
Comprise 2.0 meters of the length of thermolysis pipe, diameter is 1.0cm, 400 ℃ of the temperature of thermal oil, and back pressure valve pressure (gauge pressure) 1.0atm, gas flow is 0.5L/min.
At first open agitator and Temperature controlled heater, make the temperature of thermal oil rise to set(ting)value, opened valve k1 high pure nitrogen purging system 1 hour, drive air in the system away, then close K1.Open the K3 valve and take intrasystem nitrogen away with vacuum pump, make system reach certain vacuum tightness, then close K3.Open pressurizing valve K1, back pressure valve K4 is set as 1.0atm (gauge pressure), the silane gas for the treatment of removal of impurities enters pipeline from valve K1, the flow of adjust flux meter is 0.5L/min, in the silane preheater, enter the thermolysis pipe after the preheating, heat decomposition temperature is lower than the phosphine of silane, borine, arsine, silicoethane etc. impurity decomposes in the thermolysis pipe, then the silane gas of high temperature enters the silane gas preheater, for the silane preheating provides heat, silane after impurity decomposes enters dust collection, the solid particulate that forms in the decomposition course inside deposits, cooled silane enters into the silane gathering system by strainer, behind system run all right, to open K5 and the silane gas after purifying is sent into gas chromatograph test its purity, the silane after this removal of impurities is denoted as A1.
With embodiment 1, difference is: the temperature of thermal oil is 200 ℃, and the silane after this removal of impurities is denoted as A2.
With embodiment 1, difference is: the temperature of thermal oil is 500 ℃, and the silane after this removal of impurities is denoted as A3.
Comparative Examples 1
Adopt the method for patent CN201010148476 that silane is carried out removal of impurities,, the silane after this removal of impurities is denoted as CA1.
Testing method and result
Testing method: GB/T 15909-2009 " used in electronic industry gas silane " the results are shown in Table 1.
Table 1
Microimpurity in silane removal method provided by the invention can make the content of B, P, As, silicoethane etc. to several ppb levels under suitable processing condition, and it is remarkable that visible the method is removed B, P, As, silicoethane etc. impurity effect.Impurity-eliminating effect and the embodiment of the method for Comparative Examples are basically identical, but its energy consumption is larger.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the removal method of impurity in the silane is characterized in that, the method carries out in the thermolysis pipe removing solid impurity after the thermolysis for silane is passed into; The temperature of described thermolysis is 200-500 ℃, and the length of described thermolysis pipe is 0.5-3m, and the flow of silane is 0.1-5L/min.
2. the removal method of impurity in the silane according to claim 1 is characterized in that, carries out preheating at the silane for the treatment of removal of impurities before the thermolysis in preheater.
3. the removal method of impurity in the silane according to claim 1 is characterized in that, the silane of removing solid impurity is filtered.
4. the removal method of impurity in the described silane of any one is characterized in that according to claim 1-3, before silane is processed, removes the air in the whole equipment.
5. the removal method of impurity in the silane according to claim 1 is characterized in that, removes the method for the air in the whole equipment for passing into nitrogen first in this equipment, then vacuumizes; The described flow that passes into nitrogen is 1-5L/min, and the time is 1-3 hour, and the described rear system absolute pressure that vacuumizes is 1-10Pa.
6. an equipment that is used for method claimed in claim 1 is characterized in that, this equipment comprises thermolysis pipe and the dust collection that is communicated with thermolysis Guan Yiduan.
7. equipment according to claim 6 is characterized in that, described equipment also comprises be used to the reaction vessel that holds high temperature heat conductive oil, agitator and Temperature controlled heater; Described agitator is positioned at reaction vessel and high temperature heat conductive oil is stirred, described Temperature controlled heater is positioned at reaction vessel and high temperature heat conductive oil is carried out temperature control, described thermolysis pipe is arranged in high temperature heat conductive oil, and described dust collection is positioned at the outside of reaction vessel.
8. equipment according to claim 6 is characterized in that, described equipment also comprises preheater, and described preheater is communicated with the other end of thermolysis pipe.
9. equipment according to claim 8 is characterized in that, described equipment also comprises the under meter that places before the preheater.
10. equipment according to claim 6 is characterized in that, described equipment also is provided with strainer after dust collection, and described strainer is communicated with dust collection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012100860155A CN103359738A (en) | 2012-03-28 | 2012-03-28 | Method for removing impurities in silane and equipment for method |
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| CN2012100860155A CN103359738A (en) | 2012-03-28 | 2012-03-28 | Method for removing impurities in silane and equipment for method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980738A (en) * | 2019-12-04 | 2020-04-10 | 中国化学赛鼎宁波工程有限公司 | System and method for preparing disilane and trisilane by silane pyrolysis method |
| CN112213403A (en) * | 2019-07-11 | 2021-01-12 | 东泰高科装备科技有限公司 | Arsenic alkane online detection device and detection method |
| CN113772676A (en) * | 2021-09-28 | 2021-12-10 | 南通友拓新能源科技有限公司 | Low-pollution high-purity electronic grade polycrystalline silicon purification method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918310A (en) * | 2007-12-18 | 2010-12-15 | 琳德北美股份有限公司 | Methods of recovering silane |
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2012
- 2012-03-28 CN CN2012100860155A patent/CN103359738A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918310A (en) * | 2007-12-18 | 2010-12-15 | 琳德北美股份有限公司 | Methods of recovering silane |
Non-Patent Citations (1)
| Title |
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| 佘思明: "制取高纯硅的硅烷法", 《化学通报》, vol. 45, no. 8, 31 December 1963 (1963-12-31), pages 45 - 50 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112213403A (en) * | 2019-07-11 | 2021-01-12 | 东泰高科装备科技有限公司 | Arsenic alkane online detection device and detection method |
| CN110980738A (en) * | 2019-12-04 | 2020-04-10 | 中国化学赛鼎宁波工程有限公司 | System and method for preparing disilane and trisilane by silane pyrolysis method |
| CN110980738B (en) * | 2019-12-04 | 2021-07-27 | 中国化学赛鼎宁波工程有限公司 | System and method for preparing disilane and trisilane by silane pyrolysis method |
| CN113772676A (en) * | 2021-09-28 | 2021-12-10 | 南通友拓新能源科技有限公司 | Low-pollution high-purity electronic grade polycrystalline silicon purification method |
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Application publication date: 20131023 |