CN106883257B - Trim,ethylchlorosilane produces hexamethyldisilazane technique - Google Patents
Trim,ethylchlorosilane produces hexamethyldisilazane technique Download PDFInfo
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- CN106883257B CN106883257B CN201710038609.1A CN201710038609A CN106883257B CN 106883257 B CN106883257 B CN 106883257B CN 201710038609 A CN201710038609 A CN 201710038609A CN 106883257 B CN106883257 B CN 106883257B
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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Abstract
The invention discloses trim,ethylchlorosilanes to produce hexamethyldisilazane new process, its step are as follows: (1) trim,ethylchlorosilane being added in the reaction vessel, it is passed through ammonia again, and the mixed material in reaction vessel is flowed through reciprocation cycle, and the solid ammonium chloride of generation is deposited on filter screen；(2) hot water in ammonium chloride heating kettle is rinsed solid ammonium chloride, then flows back into ammonium chloride heating kettle, and hydrothermal solution, which is driven into centrifuge, in ammonium chloride heating kettle is separated by solid-liquid separation；(3) when the trim,ethylchlorosilane content in mother liquor dashpot≤0.5%, mother liquor is recycled, obtains product using rectification and purification.The present invention provides a kind of technical solutions of trim,ethylchlorosilane production hexamethyldisilazane new process, it is practical, labor intensity is low, superior product quality, high income, and react in byproduct of reaction reduce, the equipment of the treatment process and operating process are all fairly simple simultaneously, reduce energy consumption.
Description
Technical field
The present invention relates to trim,ethylchlorosilanes to produce hexamethyldisilazane technique.
Background technique
Hexamethyldisilazane (HMDS) is a kind of important organo-silicon compound, is led in organosilicon chemistry and organic synthesis
Domain has a wide range of applications.Hexamethyldisilazane is not only the critical materials of synthesis two silicon urea (BSU) of hexamethyl, and is to have
Common sillylation reagent in machine synthesis, has important industrial utility value.In organosilazanes chemistry, Ke Yiyong
Make to exchange with chlorosilane monomer progress chlorine, to obtain polysilazane, this method has in synthesis huge than direct logical ammonia process
Advantage.It is used as the adhesive aid of photo-induced etching agent in the semiconductor industry.Amikacin, penicillin, cephalo bacterium in medical industry
Hexamethyldisilazane is all used in the synthesis processes such as element.
Industrial HMDS is reacted and is made with ammonia in inert organic solvents using trim,ethylchlorosilane as raw material.By
It is easy product package wherein, therefore needs after the completion of reaction to anti-in the ammonium chloride particle generated during aminating reaction
Product should be mixed to be washed, separate and can just obtain product.But hydrolysis generation six easily occurs for HMDS in water-washing process
Tetramethyldisiloxane and trimethyl silanol cause the yield of purpose product to reduce.
Summary of the invention
Present invention aims at a kind of trim,ethylchlorosilane production pregnancy is provided for deficiency of the prior art
The technical solution of base disilazane technique, method is simple, labor intensity is low, superior product quality, high income, and anti-in reaction
By-product is answered to reduce, while the equipment of the treatment process and operating process are all fairly simple, operation automation, resources circulation benefit
With effectively save cost reduces energy consumption, improves economic benefit.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that trim,ethylchlorosilane produces two silicon of hexamethyl
Azane technique, it is characterised in that the following steps are included:
(1) trim,ethylchlorosilane is added in the reaction vessel, is stirred evenly after adding, mixing time is 15~30min,
Brine ice is added after stirring into the collet on the outside of reaction vessel and carries out cooling down processing, until the temperature in reaction vessel
Degree is down to 60~80 DEG C, opens stock discharge pump, so that trim,ethylchlorosilane is flowed into mother liquor surge tank by first filter,
It is pumped back in reaction vessel by mother liquor feed back again, whole process circulation carries out；
(2) ammonia is passed through into reaction vessel, by controlling reaction temperature, so that the trim,ethylchlorosilane in reaction vessel
The mixed slurry for generating liquid hexamethyldisilazane and solid ammonium chloride is reacted with ammonia, mixed slurry is pumped by stock discharge
Effect, enter in first filter, then be flowed into mother liquor surge tank, so that solid ammonium chloride is deposited on first filter
On filter screen；
(3) when stock discharge pump discharge pressure reaches 0.4Mpa, it is switched to the second filter, at this time ammonium chloride heating kettle
In store 80 DEG C of hot water, hot water is driven into the first filter for filling solid ammonium chloride by ammonium chloride feed pump, then
It is returned in ammonium chloride heating kettle by first filter, circulation is repeated, until the solid ammonium chloride quilt in first filter
When being completely dissolved, ammonium chloride feed pump is closed, stops flushing of the hot water to first filter, then be passed through nitrogen into first filter
Gas is purged, and the time that is passed through of nitrogen ensures in 5~10min；
(4) similarly, when stock discharge pump discharge pressure reaches 0.4MPa again, first filter, ammonium chloride are switched to
Hot water in heating kettle is driven into the second filter for filling solid ammonium chloride, by ammonium chloride feed pump using second
Filter returns in ammonium chloride heating kettle, and circulation is repeated, until the solid ammonium chloride in the second filter is completely dissolved
When, ammonium chloride feed pump is closed, stops flushing of the hot water to the second filter, then be passed through nitrogen into the second filter and blown
It sweeps, the time that is passed through of nitrogen ensures so to recycle repeatedly in 5~10min；
(5) it moves in circles 3 times after rinsing, hydrothermal solution reaches saturation in ammonium chloride heating kettle, opens ammonium chloride at this time and gives
The hot saturated solution of ammonium chloride is driven into centrifuge by material pump, switch valve by ammonium chloride cooler, the filtrate stream after separation
It returns in ammonium chloride heating kettle, the ammonium chloride filter cake isolated repeatedly, adds ammonium chloride as byproduct, dry storage, circulation
The aqueous ammonium chloride solution of heat saturation is changed into the solution after dilution in hot kettle, to continue to rinse first filter and the second filtering
Device；
(6) the trim,ethylchlorosilane content in sampling analysis mother liquor dashpot, when trim,ethylchlorosilane content≤0.5%
When, it is filling using mother liquor as crude product by switching crude product filling valve and mother liquor reflux valve, it is obtained using subsequent rectification and purification
Big mother liquor reflux valve is opened, is turned down when trim,ethylchlorosilane content increases in mother liquor dashpot to hexamethyldisilazane product
Crude product filling valve, otherwise when trim,ethylchlorosilane content reduces in mother liquor dashpot, mother liquor reflux valve is turned down, big thick production is opened
Product filling valve, by rationally controlling the valve size of crude product filling valve and mother liquor reflux valve, so that hexamethyldisilazane produces
The recovery rate of product is high, and product purity is also high；
(7) after mother liquor is filled out as crude product, the material in reaction vessel can be reduced, and be continued into reaction vessel
Raw material trim,ethylchlorosilane is supplemented, keeps liquid level in reaction vessel constant, while not stopping to be passed through ammonia, and control reaction vessel
Pressure is 10~60kpa；
(8) hexamethyldisilazane product is brought into remaining solid ammonium chloride in first filter and the second filter,
It is entered in ammonium chloride heating kettle together after rinsing, and as the accumulative of time swims in ammonium chloride heating kettle upper layer,
Periodically the floating material on ammonium chloride heating kettle upper layer is recycled, reduces the waste of resource.
Further, in step (1), reaction vessel is reaction kettle, and the operating temperature of reaction kettle is 100 DEG C~150 DEG C.
Further, in step (2), reaction temperature is 40~55 DEG C, and the reaction time is 0.5~1.2h.
Further, in step (2), the rate that is passed through of ammonia is 0.5~1.5L/min, ammonia and trim,ethylchlorosilane
Molal weight ratio is (3.0~3.5): 2.
The reactional equation of trim,ethylchlorosilane production hexamethyldisilazane technique of the invention is as follows:
(CH3)3SiCl+NH3→(CH3)3SiNHSi(CH3)3+NH4Cl
Compared with prior art, process is simple, labor intensity is low, quality of finished is obviously improved, yield by the present invention
It increases substantially, byproduct of reaction reduces in product.And the present invention does not add solvent in the reaction, only adds in reaction kettle
Enter the trim,ethylchlorosilane of requirement, stir, be passed directly into ammonia and reacted, and speed is passed through by strict control ammonia
The intake of rate and ammonia avoids the waste of resource while ensuring reaction rate.With the progress of reaction, ammonium chloride is solid
Body is more and more, when material becomes paste gradually, and circulating with mixed slurry, so that solid ammonium chloride quilt in mixed slurry
It is deposited on the filter screen of first filter, so that solid ammonium chloride is separated with liquid hexamethyldisilazane, and liquid
Hexamethyldisilazane flows back into reaction kettle that the reaction was continued using mother liquor surge tank, and W-response process moves in circles, directly
To reaction end, reaction rate is effectively increased, whole operation also enhanced convenience.Simultaneously in reaction carries out, when the first mistake
When solid ammonium chloride in filter deposits to certain quantity, without stopping reaction, it need to will only continue the solid ammonium chloride of production
It is passed into the second filter and is deposited, it, not only can be to avoid by being used alternatingly for first filter and the second filter
The interruption of reaction effectively improves reaction rate, and can operate more simple in order to the recovery processing of subsequent ammonium chloride again
Just.While first filter and the second filter switch over, ammonium chloride heating kettle is by hot water to depositing to a fixed number
The filter of amount solid ammonium chloride move in circles washing away, so that solid ammonium chloride is completely dissolved, enters ammonium chloride and adds
In hot kettle, it is separated by solid-liquid separation using centrifuge, in the liquid reflux ammonium chloride heating kettle after separation, the ammonium chloride isolated
Filter cake carries out cycling and reutilization as byproduct, and effectively save resource reduces energy consumption, improves comprehensive utilization ratio.And by taking
Sample analyzes the trim,ethylchlorosilane content in mother liquor dashpot, and recycling mother liquor is filling as crude product, passes through subsequent rectification and purification
Reach finished product, entire simple process is easy to operate.And this method not solubilizer, and react the solid ammonium chloride generated and obtain
It timely separates and recycles, ensure that material in reactor has good mixing effect, reaction can be gone on smoothly on earth；Due to not
The concentration of solubilization dilution agent, reaction mass is high, and reaction speed faster, effectively shortens batch yield response time；Also due to not adding
Solvent, reaction kettle criticize 3~4 times of output increased or more；Due also to not needing recycling design, energy consumption and manpower is greatly saved,
Production efficiency greatly improves.
The present invention provides a kind of technical solution of trim,ethylchlorosilane production hexamethyldisilazane technique, method letters
It is single, practical, labor intensity is low, superior product quality, high income, and the byproduct of reaction in reacting reduces, while at this
The equipment of science and engineering skill and operating process are all fairly simple, operation automation, resource circulation utilization, effectively save cost, reduce energy
Consumption, improves economic benefit.
Detailed description of the invention
The present invention will be further explained below with reference to the attached drawings:
Fig. 1 is the flow chart that trim,ethylchlorosilane of the present invention produces hexamethyldisilazane technique；
In figure: 1- reaction kettle；2- collet；3- stock discharge pump 3；4- first filter 4；5- mother liquor surge tank 5；6- mother liquor
Feed back pump 6；7- filter screen 7；8- mother liquor reflux valve 8；The second filter of 9- 9；10- ammonium chloride heating kettle 10；11- superchlorination ammonium is given
Material pump 11；12- ammonium chloride cooler 12；13- centrifuge 13；14- crude product filling valve 14.
Specific embodiment
As described in Figure 1, hexamethyldisilazane technique is produced for trim,ethylchlorosilane of the present invention, comprising the following steps:
(1) trim,ethylchlorosilane is added in the reaction vessel, is stirred evenly after adding, mixing time is 15~30min,
Brine ice is added in collet 2 after stirring on the outside of reaction vessel and carries out cooling down processing, until in reaction vessel
Temperature is down to 60~80 DEG C, opens stock discharge pump 3, delays so that trim,ethylchlorosilane is flowed into mother liquor by first filter 4
Tank 5 is rushed, then is returned in reaction vessel by mother liquor feed back pump 6, whole process circulation carries out, and reaction vessel is reaction kettle 1, reaction
The operating temperature of kettle 1 is 100 DEG C~150 DEG C；
(2) ammonia is passed through into reaction vessel, by controlling reaction temperature, so that the trim,ethylchlorosilane in reaction vessel
The mixed slurry for generating liquid hexamethyldisilazane and solid ammonium chloride is reacted with ammonia, mixed slurry is pumped by stock discharge
3 effect enters in first filter 4, then is flowed into mother liquor surge tank 5, so that solid ammonium chloride is deposited on the first filtering
On the filter screen 7 of device 4, reaction temperature be 40~55 DEG C, the reaction time be 0.5~1.2h, ammonia be passed through rate be 0.5~
The molal weight ratio of 1.5L/min, ammonia and trim,ethylchlorosilane is (3.0~3.5): 2；
(3) when stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, ammonium chloride heats at this time
80 DEG C of hot water is stored in kettle 10, hot water is driven into the first filtering for filling solid ammonium chloride by ammonium chloride feed pump 11
It in device 4, is returned in ammonium chloride heating kettle 10 using first filter 4, circulation is repeated, until in first filter 4
When solid ammonium chloride is completely dissolved, ammonium chloride feed pump 11 is closed, stops flushing of the hot water to first filter 4, then toward the
It is passed through nitrogen in one filter 4 to be purged, the time that is passed through of nitrogen ensures in 5~10min；
(4) similarly, when stock discharge, which pumps 3 outlet pressures, reaches 0.4MPa again, first filter 4, chlorination are switched to
Hot water in ammonium heating kettle 10 is driven into the second filter 9 for filling solid ammonium chloride, then pass through by ammonium chloride feed pump 11
It crosses the second filter 9 to return in ammonium chloride heating kettle 10, circulation is repeated, the solid ammonium chloride in the second filter 9
When being completely dissolved, ammonium chloride feed pump is closed, stops flushing of the hot water to the second filter 9, then lead into the second filter 9
Enter nitrogen to be purged, the time that is passed through of nitrogen ensures so to recycle repeatedly in 5~10min；
(5) it moves in circles 3 times after rinsing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride at this time
The hot saturated solution of ammonium chloride is driven into centrifuge 13, after separation by feed pump 11, switch valve by ammonium chloride cooler 12
Filtrate flow back into ammonium chloride heating kettle 10, the ammonium chloride filter cake isolated is as byproduct, dry storage, circulation repeatedly,
The aqueous ammonium chloride solution of heat saturation in ammonium chloride heating kettle 10 is set to be changed into the solution after dilution, to continue to rinse the first filtering
Device 4 and the second filter 9；
(6) the trim,ethylchlorosilane content in sampling analysis mother liquor surge tank 5, when trim,ethylchlorosilane content≤0.5%
When, it is filling using mother liquor as crude product by switching crude product filling valve 14 and mother liquor reflux valve 8, it is mentioned using subsequent rectifying
It is pure to obtain hexamethyldisilazane product, when trim,ethylchlorosilane content increases in mother liquor surge tank 5, open big mother liquor reflux valve
8, crude product filling valve 14 is turned down, otherwise when trim,ethylchlorosilane content reduces in mother liquor dashpot, turn down mother liquor reflux valve
8, big crude product filling valve 14 is opened, by rationally controlling the valve size of crude product filling valve 14 and mother liquor reflux valve 8, so that six
The recovery rate of methyl disilazane product is high, and product purity is also high；
(7) after mother liquor is filled out as crude product, the material in reaction vessel can be reduced, and be continued into reaction vessel
Raw material trim,ethylchlorosilane is supplemented, keeps liquid level in reaction vessel constant, while not stopping to be passed through ammonia, and control reaction vessel
Pressure is 10~60kpa；
(8) hexamethyldisilazane production is brought in first filter 4 and the second filter 9 in remaining solid ammonium chloride into
Product enter in ammonium chloride heating kettle 10 together after rinsing, and as the accumulative of time swims in ammonium chloride heating kettle
10 upper layers periodically recycle the floating material on 10 upper layer of ammonium chloride heating kettle, reduce the waste of resource.
By the following examples to the present invention carry out more specific description, but the present invention is not limited to embodiment.
Embodiment 1
200kg trim,ethylchlorosilane, stirring, mixing time 15min, toward anti-after stirring are added in reaction kettle 1
It answers and brine ice progress cooling down processing is added in the collet in 1 outside of kettle, until the temperature in reaction kettle 1 is down to 60 DEG C, unlatching
Stock discharge pump 3, so that trim,ethylchlorosilane is flowed into mother liquor surge tank 5 by first filter 4, returns in reaction kettle 1.
Ammonia is passed through into reaction kettle 1 simultaneously, the rate that is passed through of ammonia is 0.5L/min, the molal weight of ammonia and trim,ethylchlorosilane
Than for 3.0:2, reaction temperature is 40 DEG C, reaction time 0.5h, so that the trim,ethylchlorosilane and ammonia in reaction kettle 1 are anti-
The mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride should be generated, mixed slurry is flowed by first filter 4
Mother liquor surge tank 5, so that solid ammonium chloride is deposited on the filter screen 7 of first filter 4.
When stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, in ammonium chloride heating kettle 10
80 DEG C of hot water is stored, hot water is driven into the first filter 4 for filling solid ammonium chloride, is returned using first filter 4
Into ammonium chloride heating kettle 10, circulation is repeated, and when the solid ammonium chloride in first filter 4 is completely dissolved, is stopped
It only rinses, then is passed through nitrogen into first filter 4 and is purged, the time that is passed through of nitrogen ensures similarly, to work as slurry in 5min
When 3 outlet pressure of discharging pump reaches 0.4MPa again, it is switched to first filter 4, is so recycled repeatedly.It moves in circles 3 times and rushes
After washing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride feed pump, switch valve, by ammonium chloride at this time
Hot saturated solution is driven into centrifuge 13, and the filtrate after separation flow back into ammonium chloride heating kettle 10, the ammonium chloride isolated
Filter cake is as byproduct recycling and reusing.
Trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve 14 and mother liquor reflux valve 8 are crossed, it is filling using mother liquor as crude product, it is obtained using subsequent rectification and purification
Hexamethyldisilazane product.And raw material trim,ethylchlorosilane is supplemented into reaction kettle 1 incessantly, is kept in reaction kettle 1
Liquid level is constant, while not stopping to be passed through ammonia, and control 1 pressure of reaction kettle is 15kpa, and periodically on ammonium chloride heating kettle 10
The floating material of layer is recycled.
After the present embodiment operation, the hexamethyldisilazane product 179.98kg of content >=99%, the yield of finished product are obtained
Reach 87.99%.
Embodiment 2
250kg trim,ethylchlorosilane, stirring, mixing time 18min, toward anti-after stirring are added in reaction kettle 1
It answers and brine ice progress cooling down processing is added in the collet in 1 outside of kettle, until the temperature in reaction kettle 1 is down to 70 DEG C, unlatching
Stock discharge pump 3, so that trim,ethylchlorosilane is flowed into mother liquor surge tank 5 by first filter 4, returns in reaction kettle 1.
Ammonia is passed through into reaction kettle 1 simultaneously, the rate that is passed through of ammonia is 0.8L/min, the molal weight of ammonia and trim,ethylchlorosilane
Than for 3.1:2, reaction temperature is 45 DEG C, reaction time 0.8h, so that the trim,ethylchlorosilane and ammonia in reaction kettle 1 are anti-
The mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride should be generated, mixed slurry is flowed by first filter 4
Mother liquor surge tank 5, so that solid ammonium chloride is deposited on the filter screen 7 of first filter 4.
When stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, in ammonium chloride heating kettle 10
80 DEG C of hot water is stored, hot water is driven into the first filter 4 for filling solid ammonium chloride, is returned using first filter 4
Into ammonium chloride heating kettle 10, circulation is repeated, and when the solid ammonium chloride in first filter 4 is completely dissolved, is stopped
It only rinses, then is passed through nitrogen into first filter 4 and is purged, the time that is passed through of nitrogen ensures similarly, to work as slurry in 6min
When 3 outlet pressure of discharging pump reaches 0.4MPa again, it is switched to first filter 4, is so recycled repeatedly.It moves in circles 3 times and rushes
After washing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride feed pump, switch valve, by ammonium chloride at this time
Hot saturated solution is driven into centrifuge 13, and the filtrate after separation flow back into ammonium chloride heating kettle 10, the ammonium chloride isolated
Filter cake is as byproduct recycling and reusing.
Trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve 14 and mother liquor reflux valve 8 are crossed, it is filling using mother liquor as crude product, it is obtained using subsequent rectification and purification
Hexamethyldisilazane product.And raw material trim,ethylchlorosilane is supplemented into reaction kettle 1 incessantly, is kept in reaction kettle 1
Liquid level is constant, while not stopping to be passed through ammonia, and control 1 pressure of reaction kettle is 23kpa, and periodically on ammonium chloride heating kettle 10
The floating material of layer is recycled.
After the present embodiment operation, the hexamethyldisilazane product of content >=99% is obtained, the yield of finished product reaches
85.75%.
Embodiment 3
320kg trim,ethylchlorosilane, stirring, mixing time 20min, toward anti-after stirring are added in reaction kettle 1
It answers and brine ice progress cooling down processing is added in the collet in 1 outside of kettle, until the temperature in reaction kettle 1 is down to 73 DEG C, unlatching
Stock discharge pump 3, so that trim,ethylchlorosilane is flowed into mother liquor surge tank 5 by first filter 4, returns in reaction kettle 1.
Ammonia is passed through into reaction kettle 1 simultaneously, the rate that is passed through of ammonia is 1L/min, the molal weight ratio of ammonia and trim,ethylchlorosilane
For 3.3:2, reaction temperature is 48 DEG C, reaction time 1h, so that the trim,ethylchlorosilane in reaction kettle 1 reacts generation with ammonia
The mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride, mixed slurry are flowed into mother liquor by first filter 4 and delay
Tank 5 is rushed, so that solid ammonium chloride is deposited on the filter screen 7 of first filter 4.
When stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, in ammonium chloride heating kettle 10
80 DEG C of hot water is stored, hot water is driven into the first filter 4 for filling solid ammonium chloride, is returned using first filter 4
Into ammonium chloride heating kettle 10, circulation is repeated, and when the solid ammonium chloride in first filter 4 is completely dissolved, is stopped
It only rinses, then is passed through nitrogen into first filter 4 and is purged, the time that is passed through of nitrogen ensures similarly, to work as slurry in 8min
When 3 outlet pressure of discharging pump reaches 0.4MPa again, it is switched to first filter 4, is so recycled repeatedly.It moves in circles 3 times and rushes
After washing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride feed pump, switch valve, by ammonium chloride at this time
Hot saturated solution is driven into centrifuge 13, and the filtrate after separation flow back into ammonium chloride heating kettle 10, the ammonium chloride isolated
Filter cake is as byproduct recycling and reusing.
Trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve 14 and mother liquor reflux valve 8 are crossed, it is filling using mother liquor as crude product, it is obtained using subsequent rectification and purification
Hexamethyldisilazane product.And raw material trim,ethylchlorosilane is supplemented into reaction kettle 1 incessantly, is kept in reaction kettle 1
Liquid level is constant, while not stopping to be passed through ammonia, and control 1 pressure of reaction kettle is 30kpa, and periodically on ammonium chloride heating kettle 10
The floating material of layer is recycled.
After the present embodiment operation, the hexamethyldisilazane product of content >=99% is obtained, the yield of finished product reaches
90.05%.
Embodiment 4
360kg trim,ethylchlorosilane, stirring, mixing time 30min, toward anti-after stirring are added in reaction kettle 1
It answers and brine ice progress cooling down processing is added in the collet in 1 outside of kettle, until the temperature in reaction kettle 1 is down to 77 DEG C, unlatching
Stock discharge pump 3, so that trim,ethylchlorosilane is flowed into mother liquor surge tank 5 by first filter 4, returns in reaction kettle 1.
Ammonia is passed through into reaction kettle 1 simultaneously, the rate that is passed through of ammonia is 1.2L/min, the molal weight of ammonia and trim,ethylchlorosilane
Than for 3.5:2, reaction temperature is 52 DEG C, reaction time 1.2h, so that the trim,ethylchlorosilane and ammonia in reaction kettle 1 are anti-
The mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride should be generated, mixed slurry is flowed by first filter 4
Mother liquor surge tank 5, so that solid ammonium chloride is deposited on the filter screen 7 of first filter 4.
When stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, in ammonium chloride heating kettle 10
80 DEG C of hot water is stored, hot water is driven into the first filter 4 for filling solid ammonium chloride, is returned using first filter 4
Into ammonium chloride heating kettle 10, circulation is repeated, and when the solid ammonium chloride in first filter 4 is completely dissolved, is stopped
It only rinses, then is passed through nitrogen into first filter 4 and is purged, the time that is passed through of nitrogen ensures similarly, to work as slurry in 10min
When material 3 outlet pressure of discharging pump reaches 0.4MPa again, it is switched to first filter 4, is so recycled repeatedly.It moves in circles 3 times
After flushing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride feed pump, switch valve, by chlorination at this time
The hot saturated solution of ammonium is driven into centrifuge 13, and the filtrate after separation flow back into ammonium chloride heating kettle 10, the chlorination isolated
Ammonium filter cake is as byproduct recycling and reusing.
Trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve 14 and mother liquor reflux valve 8 are crossed, it is filling using mother liquor as crude product, it is obtained using subsequent rectification and purification
Hexamethyldisilazane product.And raw material trim,ethylchlorosilane is supplemented into reaction kettle 1 incessantly, is kept in reaction kettle 1
Liquid level is constant, while not stopping to be passed through ammonia, and control 1 pressure of reaction kettle is 38kpa, and periodically on ammonium chloride heating kettle 10
The floating material of layer is recycled.
After the present embodiment operation, the hexamethyldisilazane product of content >=99% is obtained, the yield of finished product reaches
93.05%.
Embodiment 5
410kg trim,ethylchlorosilane, stirring, mixing time 28min, toward anti-after stirring are added in reaction kettle 1
It answers and brine ice progress cooling down processing is added in the collet in 1 outside of kettle, until the temperature in reaction kettle 1 is down to 80 DEG C, unlatching
Stock discharge pump 3, so that trim,ethylchlorosilane is flowed into mother liquor surge tank 5 by first filter 4, returns in reaction kettle 1.
Ammonia is passed through into reaction kettle 1 simultaneously, the rate that is passed through of ammonia is 1.5L/min, the molal weight of ammonia and trim,ethylchlorosilane
Than for 3.5:2, reaction temperature is 55 DEG C, reaction time 0.9h, so that the trim,ethylchlorosilane and ammonia in reaction kettle 1 are anti-
The mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride should be generated, mixed slurry is flowed by first filter 4
Mother liquor surge tank 5, so that solid ammonium chloride is deposited on the filter screen 7 of first filter 4.
When stock discharge, which pumps 3 outlet pressures, reaches 0.4Mpa, it is switched to the second filter 9, in ammonium chloride heating kettle 10
80 DEG C of hot water is stored, hot water is driven into the first filter 4 for filling solid ammonium chloride, is returned using first filter 4
Into ammonium chloride heating kettle 10, circulation is repeated, and when the solid ammonium chloride in first filter 4 is completely dissolved, is stopped
It only rinses, then is passed through nitrogen into first filter 4 and is purged, the time that is passed through of nitrogen ensures similarly, to work as slurry in 8min
When 3 outlet pressure of discharging pump reaches 0.4MPa again, it is switched to first filter 4, is so recycled repeatedly.It moves in circles 3 times and rushes
After washing, hydrothermal solution reaches saturation in ammonium chloride heating kettle 10, opens ammonium chloride feed pump, switch valve, by ammonium chloride at this time
Hot saturated solution is driven into centrifuge 13, and the filtrate after separation flow back into ammonium chloride heating kettle 10, the ammonium chloride isolated
Filter cake is as byproduct recycling and reusing.
Trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve 14 and mother liquor reflux valve 8 are crossed, it is filling using mother liquor as crude product, it is obtained using subsequent rectification and purification
Hexamethyldisilazane product.And raw material trim,ethylchlorosilane is supplemented into reaction kettle 1 incessantly, is kept in reaction kettle 1
Liquid level is constant, while not stopping to be passed through ammonia, and control 1 pressure of reaction kettle is 50kpa, and periodically on ammonium chloride heating kettle 10
The floating material of layer is recycled.
After the present embodiment operation, the hexamethyldisilazane product of content >=99% is obtained, the yield of finished product reaches
91.13%.
See Table 1 for details for test result:
The production result of 1 hexamethyldisilazane of table
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (2)
1. trim,ethylchlorosilane produces hexamethyldisilazane technique, which comprises the following steps:
(1) trim,ethylchlorosilane is added in the reaction vessel, is stirred evenly after adding, mixing time is 15~30min, stirring knot
Brine ice is added after beam into the collet on the outside of reaction vessel and carries out cooling down processing, until the temperature in reaction vessel is down to
60~80 DEG C, stock discharge pump is opened, so that trim,ethylchlorosilane is flowed into mother liquor surge tank by first filter, then is passed through
Mother liquor feed back is pumped back in reaction vessel, and whole process circulation carries out, and the reaction vessel is reaction kettle, the work of the reaction kettle
Making temperature is 100 DEG C~150 DEG C；
(2) ammonia is passed through into reaction vessel, by controlling reaction temperature, so that trim,ethylchlorosilane and ammonia in reaction vessel
Solid/liquid/gas reactions generate the mixed slurry of liquid hexamethyldisilazane and solid ammonium chloride, and mixed slurry passes through the work of stock discharge pump
With entering in first filter, then be flowed into mother liquor surge tank, so that solid ammonium chloride is deposited on the filtering of first filter
On the net, reaction temperature is 40~55 DEG C, and the reaction time is 0.5~1.2h；
(3) when stock discharge pump discharge pressure reaches 0.4Mpa, it is switched to the second filter, is stored up in ammonium chloride heating kettle at this time
80 DEG C of hot water has been deposited, hot water is driven into the first filter for filling solid ammonium chloride by ammonium chloride feed pump, using
First filter returns in ammonium chloride heating kettle, and circulation is repeated, until the solid ammonium chloride in first filter is complete
When dissolution, close ammonium chloride feed pump, stop flushing of the hot water to first filter, then be passed through into first filter nitrogen into
Row purging, the time that is passed through of nitrogen ensure in 5~10min；
(4) similarly, when stock discharge pump discharge pressure reaches 0.4MPa again, first filter, ammonium chloride heating are switched to
Hot water in kettle is driven into the second filter for filling solid ammonium chloride by ammonium chloride feed pump, using the second filtering
Device returns in ammonium chloride heating kettle, and circulation is repeated, and when the solid ammonium chloride in the second filter is completely dissolved, closes
Ammonium chloride feed pump is closed, stops flushing of the hot water to the second filter, then be passed through nitrogen into the second filter and purged, nitrogen
The time that is passed through of gas ensures so to recycle repeatedly in 5~10min；
(5) it moving in circles 3 times after rinsing, hydrothermal solution reaches saturation in ammonium chloride heating kettle, ammonium chloride feed pump is opened at this time,
The hot saturated solution of ammonium chloride is driven into centrifuge by switch valve by ammonium chloride cooler, and the filtrate after separation flow back into
In ammonium chloride heating kettle, as byproduct, dry storage recycles repeatedly, makes ammonium chloride heating kettle the ammonium chloride filter cake isolated
The aqueous ammonium chloride solution of middle heat saturation is changed into the solution after dilution, to continue to rinse first filter and the second filter；
(6) the trim,ethylchlorosilane content in sampling analysis mother liquor dashpot is led to when trim,ethylchlorosilane content≤0.5%
Switching crude product filling valve and mother liquor reflux valve are crossed, it is filling using mother liquor as crude product, six are obtained using subsequent rectification and purification
Methyl disilazane product opens big mother liquor reflux valve, turns down thick production when trim,ethylchlorosilane content increases in mother liquor dashpot
Product filling valve, otherwise when trim,ethylchlorosilane content reduces in mother liquor dashpot, mother liquor reflux valve is turned down, big crude product is opened and fills
Valve is filled, by rationally controlling the valve size of crude product filling valve and mother liquor reflux valve, so that hexamethyldisilazane product
Recovery rate is high, and product purity is also high；
(7) after mother liquor is filled out as crude product, the material in reaction vessel can be reduced, and continue to supplement into reaction vessel
Raw material trim,ethylchlorosilane keeps liquid level in reaction vessel constant, while not stopping to be passed through ammonia, and control reaction vessel pressure
For 10~60kpa；
(8) hexamethyldisilazane product is brought into remaining solid ammonium chloride in first filter and the second filter, pass through
It is entered in ammonium chloride heating kettle together after flushing, and as the accumulative of time swims in ammonium chloride heating kettle upper layer, periodically
The floating material on ammonium chloride heating kettle upper layer is recycled, the waste of resource is reduced.
2. trim,ethylchlorosilane according to claim 1 produces hexamethyldisilazane technique, it is characterised in that: described
In step (2), the rate that is passed through of ammonia is 0.5~1.5L/min, the molal weight of the ammonia and the trim,ethylchlorosilane
Than for (3.0~3.5): 2.
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| CN111004271A (en) * | 2019-12-31 | 2020-04-14 | 浙江硕而博化工有限公司 | Production process of hexamethyldisilazane |
| CN111732602A (en) * | 2020-05-26 | 2020-10-02 | 浙江新安化工集团股份有限公司 | Preparation method of silazane |
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