CN109796484A - A kind of method and system for abolishing ethyl orthosilicate azeotropic distillation - Google Patents
A kind of method and system for abolishing ethyl orthosilicate azeotropic distillation Download PDFInfo
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- CN109796484A CN109796484A CN201910106865.9A CN201910106865A CN109796484A CN 109796484 A CN109796484 A CN 109796484A CN 201910106865 A CN201910106865 A CN 201910106865A CN 109796484 A CN109796484 A CN 109796484A
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Abstract
The present invention provides a kind of methods for abolishing ethyl orthosilicate azeotropic distillation, specifically abolish the method that methyltriethoxysilane, methoxyl group triethoxysilane and ethyl orthosilicate are formed by azeotropism, include: S1) ethyl orthosilicate crude product is subjected to de- rectifying again, the ethyl orthosilicate after obtaining de- rectifying again；S2 it carries out taking off light rectifying after) mixing the ethyl orthosilicate after de- rectifying again with high boiling solvent, obtains taking off the ethyl orthosilicate after light rectifying；The boiling point of the high boiling solvent is more than or equal to 180 DEG C.Compared with prior art, the present invention first removes heavy constituent through de- rectifying again, carries out taking off light rectifying after then mixing with high boiling solvent, the azeotropism in distillation process can be abolished, and solvent is recovered more easily, the efficiency and yield of rectifying are improved, energy consumption and equipment investment are alleviated.
Description
Technical field
The invention belongs to technical field of semiconductors more particularly to a kind of method for abolishing ethyl orthosilicate azeotropic distillation and it is
System.
Background technique
SiO2For natural oxide film, there is critically important purposes in semiconductor processing, such as shelter impurity, grid oxygen dielectric,
Surface passivation and protection, device isolation, metallic conduction interlayer dielectric.Semiconductor technology forms SiO2The method master of oxide layer
Have thermal oxide (for the semiconductor material that can form homeostasis oxide layer), Low Pressure Chemical Vapor Deposition (LPCVD), etc.
Plasma enhanced chemical vapor sedimentation (PECVD) and aumospheric pressure cvd method (APCVD) etc., wherein due to APCVD requirement
Throughput it is big, and technique generate particle it is relatively more, at present most of semiconductor technologies be rarely employed.High-purity positive silicic acid
When ethyl ester (Tetraethyl Orthosilicate writes a Chinese character in simplified form TEOS, monomer) is used for LPCVD, the speed of silica membrane deposition
Rate can achieve 50 à/min, and the thickness uniformity of film is less than 3%, these excellent operational characteristiies and in safety in utilization side
The distinguishing feature in face, which makes it, gradually becomes the prevailing technology of cvd silicon dioxide film.
But the preparation of existing industrial goods ethyl orthosilicate be mostly after the reacting of silicon tetrachloride and ethyl alcohol rectifying obtain, due to original
Material silicon tetrachloride is reacted with the impurity participation of institute's band in ethyl alcohol, ultimately forms ethyl alcohol, triethoxysilane, methyltriethoxy silane
Alkane, methoxyl group triethoxysilane, propyl-triethoxysilicane, ethyl orthosilicate dimer, ethyl orthosilicate tripolymer etc. have
Machine silicon impurities component.Methyltriethoxysilane, methoxyl group triethoxysilane and ethyl orthosilicate can shapes in distillation process
At azeotropism, its constituents ratio substantially methyltriethoxysilane 0.04%, methoxyl group triethoxysilane when azeotropic
0.20% with ethyl orthosilicate 99.75%.This azeotropism brings bigger difficulty to rectifying purifying, especially prepares height
When the rectifying of pure TEOS, it is necessary to repeat rectifying, higher rectifying column or bigger reflux ratio, increase equipment investment and energy
Consumption, and yield is lower.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of side for abolishing ethyl orthosilicate azeotropic distillation
Method and system, this method energy consumption is lower and efficiency with higher and yield.
The present invention provides the methods for abolishing ethyl orthosilicate azeotropic distillation, comprising:
S1 ethyl orthosilicate crude product) is subjected to de- rectifying again, the ethyl orthosilicate after obtaining de- rectifying again；
S2 it carries out taking off light rectifying after) mixing the ethyl orthosilicate after de- rectifying again with high boiling solvent, obtains de- light essence
Ethyl orthosilicate after evaporating；The boiling point of the high boiling solvent is more than or equal to 185 DEG C.
Preferably, further includes:
S3 the kettle liquid obtained after the ethyl orthosilicate after light rectifying is mixed with high boiling solvent) will be taken off and carry out rectifying, obtained
High-purity ethyl orthosilicate；The boiling point of the high boiling solvent is more than or equal to 185 DEG C.
Preferably, the step S2) in high boiling solvent be each independently selected from the high boiling solvent in step S3)
One of diphenyl ether, nitrobenzene, dimethyl sulfoxide, ethylene glycol and glycerine are a variety of.
Preferably, the step S2) in the quality of high boiling solvent be ethyl orthosilicate quality after de- rectifying again
30%~80%；The step S3) in kettle liquid the mass concentration of ethyl orthosilicate 5%~20%.
Preferably, the step S3) in rectifying temperature be 100 DEG C~140 DEG C；The pressure of rectifying preferably -0.6~-
1.0bar。
Preferably, the step S1) in take off again rectifying temperature be 100 DEG C~140 DEG C；The pressure of de- rectifying again is -0.6
~-1.0bar；The quality of removing heavy constituent is the 1/5~1/12 of ethyl orthosilicate crude product quality when de- rectifying again.
Preferably, the step S2) in take off light rectifying temperature be 95 DEG C~130 DEG C；The pressure for taking off light rectifying is -0.6
~-1.0bar；The quality that light component is removed when taking off light rectifying is 1/5~1/12 of the ethyl orthosilicate quality after de- rectifying again.
The present invention also provides a kind of systems for abolishing ethyl orthosilicate azeotropic distillation, comprising:
De- heavy distillation column and high boiling solvent storage tank；
De-light rectification column；The de-light rectification column includes material feed inlet and high boiling solvent feed inlet；The de- heavy essence
Tower is evaporated to be connected with the material inlet of de-light rectification column；The high boiling solvent storage tank is connected with high boiling solvent feed inlet.
It preferably, further include rectifying column；The rectifying column includes material feed inlet and high boiling solvent feed inlet；The essence
The material feed inlet for evaporating tower is connected with de-light rectification column；The high boiling solvent feed inlet and high boiling solvent of the rectifying column store up
Tank is connected.
It preferably, further include high boiling solvent intermediate storage tank；The high boiling solvent intermediate storage tank is connected with rectifying column；
The high boiling solvent intermediate storage tank is connected with the high boiling solvent feed inlet of de-light rectification column.
The present invention provides a kind of methods for abolishing ethyl orthosilicate azeotropic distillation, specifically abolish methyltriethoxy silane
The method that alkane, methoxyl group triethoxysilane and ethyl orthosilicate are formed by azeotropism, comprising: S1) by ethyl orthosilicate
Crude product carries out de- rectifying again, the ethyl orthosilicate after obtaining de- rectifying again；S2) by after de- rectifying again ethyl orthosilicate with it is high boiling
It carries out taking off light rectifying after point solvent mixing, obtains taking off the ethyl orthosilicate after light rectifying；The boiling point of the high boiling solvent is greater than
Equal to 180 DEG C.Compared with prior art, the present invention first removes heavy constituent through de- rectifying again, after then mixing with high boiling solvent
It carries out taking off light rectifying, the azeotropism in distillation process can be abolished, and solvent is recovered more easily, improve the efficiency and receipts of rectifying
Rate alleviates energy consumption and equipment investment.
Detailed description of the invention
Fig. 1 is the structural schematic diagram provided by the invention for abolishing ethyl orthosilicate azeotropic distillation system.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of methods for abolishing ethyl orthosilicate azeotropic distillation, comprising: S1) by ethyl orthosilicate crude product
De- rectifying again is carried out, the ethyl orthosilicate after obtaining de- rectifying again；S2) by after de- rectifying again ethyl orthosilicate and higher boiling it is molten
It carries out taking off light rectifying after agent mixing, obtains taking off the ethyl orthosilicate after light rectifying；The boiling point of the high boiling solvent is more than or equal to
185℃。
The present invention first removes heavy constituent through de- rectifying again, carries out taking off light rectifying after then mixing with high boiling solvent, can break
Except the azeotropism in distillation process, and solvent is recovered more easily, improves the efficiency and yield of rectifying, alleviate energy consumption and set
Standby investment.
The present invention is not particularly limited the source of all raw materials, is commercially available.
The ethyl orthosilicate crude product is ethyl orthosilicate crude product well known to those skilled in the art, i.e., positive silicic acid second
Ester monomer, also known as ethyl orthosilicate -28, industrial goods content are generally 99.5%Wt.
Ethyl orthosilicate crude product is subjected to de- rectifying again, the ethyl orthosilicate after obtaining de- rectifying again；The de- rectifying again
Temperature be preferably 100 DEG C~140 DEG C, more preferably 105 DEG C~130 DEG C, be further preferably 105 DEG C~125 DEG C；The de- heavy essence
The pressure evaporated is preferably -0.6~-1.0bar, more preferably -0.7~-0.9bar；The condensation temperature of the de- rectifying again is preferred
It is 30~50 DEG C；Can be removed by de- rectifying again propyl-triethoxysilicane in ethyl orthosilicate, ethyl orthosilicate dimer,
The heavy constituents such as ethyl orthosilicate tripolymer；The quality of the de- removing of rectifying again heavy constituent (i.e. high boiling component) is preferably positive silicon
The 1/5~1/12 of acetoacetic ester crude product quality, more preferably 1/7~1/10；The heavy constituent of removing is preferably recycled.
It carries out taking off light rectifying after ethyl orthosilicate after de- rectifying again is mixed with high boiling solvent, obtain after taking off light rectifying
Ethyl orthosilicate；The boiling point of the high boiling solvent is more than or equal to 185 DEG C, preferably greater than or equal to 189 DEG C；The higher boiling is molten
Agent is preferably neutral flux, due to the hydrolysis properties of ethyl orthosilicate itself, therefore selects neutral flux, and the moisture in system is not
Can be too high, one of diphenyl ether, nitrobenzene, dimethyl sulfoxide, ethylene glycol and glycerine or a variety of are more preferably in the present invention,
It is further preferably diphenyl ether and/or dimethyl sulfoxide according to the physico-chemical property of solvent；By high boiling solvent to de- rectifying again after
Ethyl orthosilicate is diluted, and the quality of the high boiling solvent is preferably 30% of the ethyl orthosilicate quality after de- rectifying again
~80%, more preferably 40%~70%, it is further preferably 50%~65%；The temperature of the dehydrogenation rectifying is preferably 95 DEG C~
130 DEG C, more preferably 100 DEG C~120 DEG C；The pressure for taking off light rectifying be preferably -0.6~-1.0bar, more preferably -0.7
~-0.9bar；The temperature for taking off light rectifying condensation is preferably 30~50 DEG C；The reflux ratio for taking off light rectifying is preferably 1~
10, more preferably 2~8, it is further preferably 4~8, most preferably 6~8；Second in ethyl orthosilicate can be removed by taking off light rectifying
The light components such as alcohol, triethoxysilane, methyltriethoxysilane, methoxyl group triethoxysilane；It is described to remove when taking off light rectifying
The quality for going light component is preferably 1/5~1/12, more preferably 1/7~1/10 of the ethyl orthosilicate quality after de- rectifying again；
The concentration for taking off high boiling solvent in light distillation process can be also detected by online gas chromatographic analysis in the present invention, according to online
Analysis is as a result, be adjusted the concentration of wherein solvent.Rectifying is carried out in the presence of high boiling solvent, can abolish methyltriethoxy silane
The azeotropism that alkane, methoxyl group triethoxysilane and ethyl orthosilicate are formed, makes ethyl orthosilicate thoroughly remove light component.
It is preferred that carrying out rectifying for the kettle liquid obtained after the ethyl orthosilicate after light rectifying is mixed with high boiling solvent is taken off, obtain
High-purity ethyl orthosilicate；The rectifying preferably uses rectifying column to carry out；Ethyl orthosilicate after taking off light rectifying is preferably in rectifying column
Middle and lower part charging；The mass concentration of ethyl orthosilicate is preferably 5%~20% in the kettle liquid, more preferably 10%~
15%；The boiling point of the high boiling solvent is more than or equal to 185 DEG C, preferably greater than or equal to 189 DEG C；The high boiling solvent is preferably
Neutral flux due to the hydrolysis properties of ethyl orthosilicate itself, therefore selects neutral flux, and the moisture in system cannot be too high,
One of diphenyl ether, nitrobenzene, dimethyl sulfoxide, ethylene glycol and glycerine or a variety of are more preferably in the present invention, according to molten
The physico-chemical property of agent is further preferably diphenyl ether and/or dimethyl sulfoxide；The temperature of the rectifying is preferably 100 DEG C~140 DEG C,
More preferably 105 DEG C~130 DEG C, be further preferably 105 DEG C~125 DEG C；The pressure of the rectifying is preferably -0.6~-1.0bar,
More preferably -0.7~-0.9bar；The temperature of the rectifying condensation is preferably 30~50 DEG C；The reflux ratio of the rectifying is preferably
1~10, more preferably 2~8, it is further preferably 4~8, most preferably 6~8；Remaining solvent can be recycled to step S2) after rectifying
Middle continuation carries out taking off light rectifying with taking off the ethyl orthosilicate after light rectifying and mix.High-purity ethyl orthosilicate is being obtained by rectifying
Recycling design simultaneously, avoids another solubilizer recyclable device, reduces the investment and energy consumption of equipment.
Due to forming methyltriethoxysilane, the methoxyl group triethoxysilane of azeotropic mixture phenomenon with ethyl orthosilicate,
The boiling point of both substances is all lower than ethyl orthosilicate, therefore the present invention first removes propyl-triethoxysilicane, ethyl orthosilicate two
The heavy components such as aggressiveness, ethyl orthosilicate tripolymer add high boiling solvent dilution, abolish azeotropism, remove lighter component, return
It receives solvent and obtains high-purity ethyl orthosilicate.
The present invention also provides a kind of systems for abolishing ethyl orthosilicate azeotropic distillation, comprising: de- heavy distillation column with it is high boiling
Point solvent tank；De-light rectification column；The de-light rectification column includes material feed inlet and high boiling solvent feed inlet；The de- weight
Rectifying column is connected with the material inlet of de-light rectification column；The high boiling solvent storage tank is connected with high boiling solvent feed inlet
It is logical.
Referring to Fig. 1, Fig. 1 is the structural schematic diagram provided by the invention for abolishing ethyl orthosilicate azeotropic distillation system, wherein
V01 is ethyl orthosilicate crude product storage tank, and P01 feeds delivery pump, and T01 takes off heavy distillation column, and E01 is the reboiler of de- heavy distillation column,
P02 is pump, and V02 is heavy constituent storage tank, and E02 is the condenser of de- heavy distillation column, and V03 is solvent intermediate storage tank, and P04 follows for solvent
Ring pump, T02 are de-light rectification column, and E03 is the reboiler of de-light rectification column, and E04 is the condenser of de-light rectification column, and V04 is light
Component storage tank, P03 are the discharging pump of de-light rectification column, and T03 is rectifying column, and E05 is the reboiler of rectifying column, and E06 is rectifying column
Condenser, V05 be high-purity ethyl orthosilicate storage tank.
In the present invention, the material inlet for taking off heavy distillation column is preferably placed at middle and upper part；The tower bottom of the de- heavy distillation column is set
It is equipped with reboiler, is heated for the material in rectifying；The tower top of the de- heavy distillation column is provided with condenser；Utilize condensation
Device condensation flows back.
According to this present invention it is also preferable to include heavy constituent storage tank, the de- heavy distillation column is connected with heavy constituent storage tank, uses
In the heavy constituent for recycling de- heavy distillation column removing.
The de- heavy distillation column is preferably connected by taking off the condenser of heavy distillation column with the material inlet of de-light rectification column；
The material inlet of the de-light rectification column is preferably placed at the middle and lower part of de-light rectification column；The high boiling solvent storage tank and de- light essence
The high boiling solvent feed inlet for evaporating tower is connected.High boiling solvent enters in de-light rectification column through high boiling solvent feed inlet to be diluted
Ethyl orthosilicate after de- heavy distillation column, carries out taking off frivolous light rectifying；For detection de-light rectification column in high boiling solvent content,
It is also preferable to include detection systems；The detection system is connected with de-light rectification column, is carried out with to the kettle liquid in de-light rectification column
Analysis detection is adjusted according to the solubility that high boiling solvent in de-light rectification column is adjusted in analysis detection result；The inspection
Examining system is preferably online gas chromatographic analysis detection system.
The tower bottom of the de-light rectification column is provided with reboiler, to heated material；The tower top of the de-light rectification column is set
It is equipped with condenser, to be condensed back；According to the present invention, it is also preferable to include light component storage tank, the de-light rectification column is preferably logical
The condenser for crossing de-light rectification column is connected with light component storage tank.It is stored up after the light component condensation of removing through flow by gravity to light component
In tank.
According to the present invention, it is also preferable to include rectifying columns；The rectifying column includes that material feed inlet and high boiling solvent are fed
Mouthful；The material feed inlet of the rectifying column is connected with de-light rectification column；The high boiling solvent feed inlet and height of the rectifying column
Boiling point solvent storage tank is connected；The material feed inlet of the rectifying column is preferably placed at the middle and lower part of rectifying column, i.e., the described de- light essence
The tower bottom for evaporating tower is connected with the middle and lower part of rectifying column；The tower bottom of the rectifying column is provided with reboiler, to heated material；Institute
The tower top setting condenser for stating rectifying column, to be condensed back.
For convenient for recycled solvent, the tower bottom of the rectifying column preferably with the high boiling solvent feed inlet of de-light rectification column
It is connected.
According to the present invention, it is also preferable to include high boiling solvent intermediate storage tanks；The high boiling solvent intermediate storage tank and rectifying
Tower is connected, and is more preferably connected with the tower bottom of rectifying column, to recycle high boiling solvent；The high boiling solvent intermediate storage tank
It is connected with the high boiling solvent feed inlet of de-light rectification column, using recovered solvent to the ethyl orthosilicate in de-light rectification column
It is diluted.
According to the present invention, it is also preferable to include high-purity ethyl orthosilicate storage tanks；High-purity ethyl orthosilicate storage tank passes through essence
The condenser for evaporating tower is connected with rectifying column.
In order to further illustrate the present invention, ethyl orthosilicate is abolished to one kind provided by the invention with reference to embodiments to be total to
The method and system of boiling rectifying are described in detail.
Reagent used in following embodiment is commercially available；It is carried out using system shown in FIG. 1.
Embodiment 1
Ethyl orthosilicate crude product is from ethyl orthosilicate crude product storage tank V01 through charging delivery pump P01 from the middle and upper part of tower to de-
Heavy distillation column T01 charging, the temperature of rectifying are 120 DEG C；Pressure is -0.76bar；The condensation temperature of de- rectifying again is 30 DEG C；It returns
Stream is than being 6；Remove propyl-triethoxysilicane, the ethyl orthosilicate dimer, ethyl orthosilicate tripolymer in ethyl orthosilicate
Equal heavy components.The amount that high boiling component (heavy constituent) is removed when de- heavy distillation column T01 rectifying is the 1/10 of rectifying material.
The heavy component of tower bottom is delivered to heavy component storage tank V02 through weight-removing column discharging pump P02, and ethyl orthosilicate and lighter component pass through
Enter de-light rectification column T02 from the middle and lower part of tower after overhead condenser condensation, the temperature of rectifying is 110 DEG C；Pressure be-
0.9bar；The temperature for taking off light rectifying is 30 DEG C；Reflux ratio 8；It is added from high boiling solvent storage tank to lightness-removing column T02 tower reactor high boiling
Point solvent diphenyl ether.The concentration of solvent is 50% of the ethyl orthosilicate quality after de- rectifying again.Solvent in rectifying column T02 tower reactor
Concentration according to online gas chromatographic analysis detection obtain, according to on-line analysis as a result, being adjusted by solvent intermediate storage tank V03
The concentration of solvent in de-light rectification column T02 tower reactor.De-light rectification column T02 from overhead condenser E04 condensation slough lighter component ethyl alcohol,
The lighter components such as triethoxysilane, methyltriethoxysilane, methoxyl group triethoxysilane.When de-light rectification column T02 rectifying
The amount for removing low boiling component (light component) is preferably the 1/8 of rectifying material, and the lighter component condensed out is through flow by gravity to gently
Component storage tank V04.In the presence of high boiling solvent, methyltriethoxysilane, methoxyl group triethoxysilane and positive silicon are abolished
The azeotropic mixture phenomenon that acetoacetic ester is formed, makes ethyl orthosilicate thoroughly remove lighter component.
De-light rectification column T02 tower reactor discharges through lightness-removing column discharging pump P03 to rectifying column T03, feeds from the middle and lower part of tower, essence
The temperature evaporated is 120 DEG C；The condensation temperature of rectifying is 40 DEG C；Pressure is -0.76bar；Reflux ratio is 6；To ensure high pure silicon
The quality of acetoacetic ester, rectifying column T03 kettle liquid are the high boiling solvent containing a certain amount of ethyl orthosilicate, the matter of this ethyl orthosilicate
Concentration is 10% is measured, rectifying column T03 tower reactor conveys solvent intermediate storage tank through solvent circulating pump P04 or de-light rectification column T02 is followed
Ring uses.Overhead condenser E06 condenses to obtain the high-purity ethyl orthosilicate of product, through gas chromatographic analysis, ethyl orthosilicate
Content is 99.9993%, and product component purity reaches 5N standard.
Embodiment 2
Ethyl orthosilicate crude product is from ethyl orthosilicate crude product storage tank V01 through charging delivery pump P01 from the middle and upper part of tower to de-
Heavy distillation column T01 charging, the temperature of rectifying are 120 DEG C；Pressure is -0.76bar；The condensation temperature of de- rectifying again is 30 DEG C；It returns
Stream is than being 6；Remove propyl-triethoxysilicane, the ethyl orthosilicate dimer, ethyl orthosilicate tripolymer in ethyl orthosilicate
Equal heavy components.The amount that high boiling component (heavy constituent) is removed when de- heavy distillation column T01 rectifying is the 1/10 of rectifying material.
The heavy component of tower bottom is delivered to heavy component storage tank V02 through weight-removing column discharging pump P02, and ethyl orthosilicate and lighter component pass through
Enter de-light rectification column T02 from the middle and lower part of tower after overhead condenser condensation, the temperature of rectifying is 110 DEG C；Pressure be-
0.9bar；The temperature for taking off light rectifying is 30 DEG C；Reflux ratio 8；It is added from high boiling solvent storage tank to lightness-removing column T02 tower reactor high boiling
Point solvent ethylene glycol.The concentration of solvent is 50% of the ethyl orthosilicate quality after de- rectifying again.Solvent in rectifying column T02 tower reactor
Concentration according to online gas chromatographic analysis detection obtain, according to on-line analysis as a result, being adjusted by solvent intermediate storage tank V03
The concentration of solvent in de-light rectification column T02 tower reactor.De-light rectification column T02 from overhead condenser E04 condensation slough lighter component ethyl alcohol,
The lighter components such as triethoxysilane, methyltriethoxysilane, methoxyl group triethoxysilane.When de-light rectification column T02 rectifying
The amount for removing low boiling component (light component) is preferably the 1/8 of rectifying material, and the lighter component condensed out is through flow by gravity to gently
Component storage tank V04.In the presence of high boiling solvent, methyltriethoxysilane, methoxyl group triethoxysilane and positive silicon are abolished
The azeotropic mixture phenomenon that acetoacetic ester is formed, makes ethyl orthosilicate thoroughly remove lighter component.
De-light rectification column T02 tower reactor discharges through lightness-removing column discharging pump P03 to rectifying column T03, feeds from the middle and lower part of tower, essence
The temperature evaporated is 120 DEG C；The condensation temperature of rectifying is 40 DEG C；Pressure is -0.76bar；Reflux ratio is 6；To ensure high pure silicon
The quality of acetoacetic ester, rectifying column T03 kettle liquid are the high boiling solvent containing a certain amount of ethyl orthosilicate, the matter of this ethyl orthosilicate
Concentration is 10% is measured, rectifying column T03 tower reactor conveys solvent intermediate storage tank through solvent circulating pump P04 or de-light rectification column T02 is followed
Ring uses.Overhead condenser E06 condenses to obtain the high-purity ethyl orthosilicate of product, through gas chromatographic analysis, ethyl orthosilicate
Content is 99.9996%, and product component purity reaches 5N standard.
Embodiment 3
Ethyl orthosilicate crude product is from ethyl orthosilicate crude product storage tank V01 through charging delivery pump P01 from the middle and upper part of tower to de-
Heavy distillation column T01 charging, the temperature of rectifying are 115 DEG C；Pressure is -0.8bar；The condensation temperature of de- rectifying again is 30 DEG C；Reflux
Than being 6；Remove propyl-triethoxysilicane, ethyl orthosilicate dimer, the ethyl orthosilicate tripolymer etc. in ethyl orthosilicate
Heavy component.The amount that high boiling component (heavy constituent) is removed when de- heavy distillation column T01 rectifying is the 1/5 of rectifying material.
The heavy component of tower bottom is delivered to heavy component storage tank V02 through weight-removing column discharging pump P02, and ethyl orthosilicate and lighter component pass through
Enter de-light rectification column T02 from the middle and lower part of tower after overhead condenser condensation, the temperature of rectifying is 110 DEG C；Pressure be-
0.9bar；The temperature for taking off light rectifying is 30 DEG C；Reflux ratio 8；It is added from high boiling solvent storage tank to lightness-removing column T02 tower reactor high boiling
Point solvent diphenyl ether.The concentration of solvent is 50% of the ethyl orthosilicate quality after de- rectifying again.Solvent in rectifying column T02 tower reactor
Concentration according to online gas chromatographic analysis detection obtain, according to on-line analysis as a result, being adjusted by solvent intermediate storage tank V03
The concentration of solvent in de-light rectification column T02 tower reactor.De-light rectification column T02 from overhead condenser E04 condensation slough lighter component ethyl alcohol,
The lighter components such as triethoxysilane, methyltriethoxysilane, methoxyl group triethoxysilane.When de-light rectification column T02 rectifying
The amount for removing low boiling component (light component) is preferably the 1/8 of rectifying material, and the lighter component condensed out is through flow by gravity to gently
Component storage tank V04.In the presence of high boiling solvent, methyltriethoxysilane, methoxyl group triethoxysilane and positive silicon are abolished
The azeotropic mixture phenomenon that acetoacetic ester is formed, makes ethyl orthosilicate thoroughly remove lighter component.
De-light rectification column T02 tower reactor discharges through lightness-removing column discharging pump P03 to rectifying column T03, feeds from the middle and lower part of tower, essence
The temperature evaporated is 120 DEG C；The condensation temperature of rectifying is 40 DEG C；Pressure is -0.76bar；Reflux ratio is 6；To ensure high pure silicon
The quality of acetoacetic ester, rectifying column T03 kettle liquid are the high boiling solvent containing a certain amount of ethyl orthosilicate, the matter of this ethyl orthosilicate
Concentration is 5% is measured, rectifying column T03 tower reactor conveys solvent intermediate storage tank through solvent circulating pump P04 or de-light rectification column T02 is recycled
It uses.Overhead condenser E06 condenses to obtain the high-purity ethyl orthosilicate of product, and through gas chromatographic analysis, ethyl orthosilicate contains
Amount is 99.9992%, and product component purity reaches 5N standard.
Claims (10)
1. a kind of method for abolishing ethyl orthosilicate azeotropic distillation characterized by comprising
S1 ethyl orthosilicate crude product) is subjected to de- rectifying again, the ethyl orthosilicate after obtaining de- rectifying again；
S2 it carries out taking off light rectifying after) mixing the ethyl orthosilicate after de- rectifying again with high boiling solvent, obtain after taking off light rectifying
Ethyl orthosilicate；The boiling point of the high boiling solvent is more than or equal to 185 DEG C.
2. the method according to claim 1, wherein further include:
S3 the kettle liquid obtained after the ethyl orthosilicate after light rectifying is mixed with high boiling solvent) will be taken off and carry out rectifying, obtained high-purity
Ethyl orthosilicate；The boiling point of the high boiling solvent is more than or equal to 185 DEG C.
3. according to the method described in claim 2, the it is characterized in that, step S2) in high boiling solvent and step S3) in
High boiling solvent be each independently selected from one of diphenyl ether, nitrobenzene, dimethyl sulfoxide, ethylene glycol and glycerine or more
Kind.
4. according to the method described in claim 2, the it is characterized in that, step S2) in the quality of high boiling solvent be de- weight
30%~80% of ethyl orthosilicate quality after rectifying；The step S3) in the mass concentration of ethyl orthosilicate in kettle liquid
5%~20%.
5. according to the method described in claim 2, the it is characterized in that, step S3) in the temperature of rectifying be 100 DEG C~140
℃；The pressure of rectifying is preferably -0.6~-1.0bar.
6. the method according to claim 1, wherein the step S1) in take off the temperature of rectifying again be 100 DEG C~
140℃；The pressure of de- rectifying again is -0.6~-1.0bar；The quality of removing heavy constituent is that ethyl orthosilicate is thick when de- rectifying again
The 1/5~1/12 of quality.
7. the method according to claim 1, wherein the step S2) in take off the temperature of light rectifying be 95 DEG C~
130℃；The pressure for taking off light rectifying is -0.6~-1.0bar；The quality of removing light component is after taking off rectifying again when taking off light rectifying
The 1/5~1/12 of ethyl orthosilicate quality.
8. a kind of system for abolishing ethyl orthosilicate azeotropic distillation characterized by comprising
De- heavy distillation column and high boiling solvent storage tank；
De-light rectification column；The de-light rectification column includes material feed inlet and high boiling solvent feed inlet；The de- heavy distillation column
It is connected with the material inlet of de-light rectification column；The high boiling solvent storage tank is connected with high boiling solvent feed inlet.
9. system according to claim 8, which is characterized in that further include rectifying column；The rectifying column includes material charging
Mouth and high boiling solvent feed inlet；The material feed inlet of the rectifying column is connected with de-light rectification column；The height of the rectifying column
Boiling point solvent feed inlet is connected with high boiling solvent storage tank.
10. system according to claim 9, which is characterized in that further include high boiling solvent intermediate storage tank；The higher boiling
Solvent intermediate storage tank is connected with rectifying column；The high boiling solvent intermediate storage tank and the high boiling solvent of de-light rectification column are fed
Mouth is connected.
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| KR20050099246A (en) * | 2004-04-09 | 2005-10-13 | 주식회사 케이씨씨 | Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope |
| CN101244974A (en) * | 2007-02-15 | 2008-08-20 | 中国石油化工股份有限公司 | Method for one-section abstraction distillation separation cracking carbon 5-cut fraction |
| CN101265245A (en) * | 2008-04-22 | 2008-09-17 | 天津大学 | Continuous distillation method and device for refining furfuryl alcohol |
| CN103601751A (en) * | 2013-11-18 | 2014-02-26 | 上海晶纯生化科技股份有限公司 | Preparation method of high-purity tetraethyl silicate |
| CN108285466A (en) * | 2018-03-06 | 2018-07-17 | 宁夏胜蓝化工环保科技有限公司 | The method for preparing ethyl orthosilicate in high yield |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050099246A (en) * | 2004-04-09 | 2005-10-13 | 주식회사 케이씨씨 | Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope |
| CN101244974A (en) * | 2007-02-15 | 2008-08-20 | 中国石油化工股份有限公司 | Method for one-section abstraction distillation separation cracking carbon 5-cut fraction |
| CN101265245A (en) * | 2008-04-22 | 2008-09-17 | 天津大学 | Continuous distillation method and device for refining furfuryl alcohol |
| CN103601751A (en) * | 2013-11-18 | 2014-02-26 | 上海晶纯生化科技股份有限公司 | Preparation method of high-purity tetraethyl silicate |
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