CN106517118A - Preparation device and method of electronic grade red phosphorus - Google Patents
Preparation device and method of electronic grade red phosphorus Download PDFInfo
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- CN106517118A CN106517118A CN201610981657.XA CN201610981657A CN106517118A CN 106517118 A CN106517118 A CN 106517118A CN 201610981657 A CN201610981657 A CN 201610981657A CN 106517118 A CN106517118 A CN 106517118A
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- red phosphorus
- warm area
- ampoule
- thermocouple
- pressure
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
- C01B25/023—Preparation of phosphorus of red phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to a preparation device of electronic grade red phosphorus. The preparation device comprises a pressure vessel, a heater, a reaction device and a vacuum pump. The adopted preparation device and method of electronic grade red phosphorus have the beneficial effects that the process of transformation of yellow phosphorus to red phosphorus is safe and controllable; as the airtight reaction device is adopted, the transformation rate of yellow phosphorus is high; a quartz vessel is used as the reaction vessel and has quite stable properties under the reaction temperature, so the electronic grade red phosphorus product can not be polluted and the purity of obtained electronic grade red phosphorus can be more than or equal to 99.9999%.
Description
Technical field
The present invention relates to a kind of yellow phosphorus is converted into the method and device of red phosphorus, more particularly to a kind of preparation of electronic grade red phosphorus
Device and method.
Background technology
By peony, brown to purple, general big crystal is in purple to red phosphorus color, and powdery solid is in peony less than 673K
By yellow phosphorus（White phosphorus）It is transformed.Yellow phosphorus is compared, red phosphorus is stable at normal temperatures, be difficult to react with oxygen, its ignition point is about 240
℃。
Electronic grade red phosphorus are mainly used in synthesizing the semi-conducting materials such as InP, GaP, due between red phosphorus and yellow phosphorus and different
There is the transforming relationship of complexity between the red phosphorus of form, it is difficult to pass through directly to purify low-grade red phosphorus that electronic grade red phosphorus are obtained,
Widespread practice is to obtain highly purified yellow phosphorus by chemically and physically method at present, and then heating yellow phosphorus under a certain pressure makes
Which is converted into red phosphorus.Chinese invention patent CN101214935B is referred to, which utilizes PCl3As raw material, after purification, obtain 6N's
Then 6N yellow phosphorus be converted into 6N red phosphorus in certain pressure with a temperature of by yellow phosphorus, and conversion temperature is finally controlled at 300 DEG C, conversion
During the inert gas of 4 ~ 8atm has been filled into conversion pot, charge operation is relevant with kettle temperature is converted.It is chemical according to Lan Shi
The saturated vapor of handbook related data yellow phosphorus is pressed in 300 DEG C for 1.46atm, it is seen that the theoretical value of phosphorous vapor and actual value difference compared with
Greatly, the method employed in patent excessively depends on experience, and after system changes, it is necessary to gas replenishment process is explored again, is existed very
Big limitation.Chinese invention patent CN102556988B is referred to, yellow phosphorus is converted under the normal pressure described in the patent of invention
There is following defect in the method for red phosphorus：Under conversion temperature, the vapour pressure of yellow phosphorus is larger, it is difficult to ensure that all of phosphorous vapor is cold
Solidifying, conversion ratio is relatively low, and phosphorus loss amount is larger；Transformation time is longer, and production efficiency is relatively low, it is difficult to scale industrial production.
《Yellow phosphorus is converted into explosion cause analysis during red phosphorus》Red phosphorus reforming unit described in one text is to adopt argon gas
Used as sealing and shielding gas, argon gas is located above red phosphorus, seals phosphorous vapor, is provided with condenser and escapes out for catching above argon gas
Phosphorous vapor, the device still suffers from problems with：Condensation efficiency is relatively low, and more phosphorous vapor is directly entered offgas duct, causes a large amount of
The loss of phosphorus；It is dangerous higher in building-up process, it is easy to cause phosphorous vapor burning, blast；It is higher to temperature control requirement, work
The more complicated technology production difficult to realize of skill.
In addition, the chemical property of phosphorus is enlivened relatively, almost binary phosphide can be formed with all of element, therefore to yellow phosphorus
It is converted into the pressure vessel used by red phosphorus and is accomplished by special requirement, in particular for makes the material of pressure vessel, material used
Material can neither polluted product, the temperature required and pressure of conversion must be reached again, although adopting the container that metal material makes can be with
Pressure required for conversion is provided, but it is unavoidable to product generation pollution；It is difficult again to meet conversion process using silica ware merely
Requirement to pressure.
Therefore, it is necessary to redesign a kind of preparation facilities and method of electronic grade red phosphorus.
The content of the invention
It is an object of the invention to solve the drawbacks described above of prior art presence, there is provided one kind can be kept the safety in production and low cost
The preparation facilities and method of honest and clean electronic grade red phosphorus.
To realize object defined above, the present invention is adopted the following technical scheme that：A kind of preparation facilities of electronic grade red phosphorus, including：
Pressure vessel, the pressure vessel include the air inlet for inflation, the gas outlet for deflation, the pressure of detection pressure
Table, the flange for sealing, support and vessel；
Heater, the heater are located in pressure vessel, and the heater includes that the first thermocouple, the second thermocouple, one add
Hot platform and a controller, first thermocouple, the second thermocouple are spaced apart from each other and are embedded in heating platform and fix, described to add
Hot platform is fixed on support, and the heating platform includes the first heater strip and the second heater strip, and the controller controls to be used for
First thermocouple of thermometric, the second thermocouple；
Reaction unit, the reaction unit be placed on heating platform it is fixed, the reaction unit include ampoule bottle, quartz diaphragm,
Displacement transducer and fixture, the ampoule bottle are formed by connecting by quartz ampoule and quartzy pipe cap, one end of the quartzy pipe cap
Including an inlet, the other end of the quartzy pipe cap is connected to form a chamber with quartz ampoule, extends before and after the chamber, described
Chamber is divided into reaction chamber and mating cavity by quartz diaphragm, and institute's displacement sensors include sensor body and the aobvious system of control, institute
State sensor body to be fixed by fixture, in mating cavity against quartz diaphragm, the control shows system and passes the sensor body
Sensor body is electrically connected with, and first heater strip and the second heater strip close on quartz diaphragm and reaction chamber respectively；
And the vavuum pump vacuumized for pressure vessel.
As a further improvement on the present invention, the heater also includes some heat-preservation cottons for ampoule bottle insulation.
As a further improvement on the present invention, the thickness of the quartz diaphragm is 2 ~ 4mm, when the pressure reduction of quartz diaphragm both sides
For 1atm when, the shape of quartz diaphragm is changed into 3 ~ 6 μm.
As a further improvement on the present invention, pass through corrugated flexible hose between the vavuum pump and pressure vessel and KF joints connect
Connect.
As a further improvement on the present invention, the vavuum pump is rotary vane mechanical pump.
As a further improvement on the present invention, first thermocouple and the second thermocouple are K-type thermocouple.
A kind of preparation method of electronic grade red phosphorus is proposed simultaneously, using the preparation facilities of above-mentioned electronic grade red phosphorus, including
Following steps：
S1：Quartz ampoule, quartzy pipe cap are cleaned up and dried, quartz ampoule and quartzy pipe cap are welded together to form into ampoule
Bottle；
S2：Inert gas replacement air is passed through into ampoule bottle, after replacing completely, 6N yellow phosphorus ampoule is injected into into by inlet
In bottle, when yellow phosphorus liquid level is close to inlet, stop plus yellow phosphorus；
S3：The inlet sealing of the ampoule bottle equipped with yellow phosphorus, during being somebody's turn to do, still inert gas is passed through into ampoule bottle；
S4：After completing tube sealing, ampoule bottle is put on heating platform, fixes the first thermocouple and the second thermocouple；Close pressure
The flange of container, opens vavuum pump and is evacuated to the pressure in pressure vessel less than 1mbar；It is sensor body is solid using fixture
Determine, and complete the abutting of sensor body and quartz diaphragm, complete the debugging of displacement transducer；
S5：First heater strip and the second heater strip close on quartz diaphragm and reaction chamber, first heater strip and respectively
The first warm area and the second warm area are formed in heating platform and ampoule bottle when two heater strips are heated, controller, the first thermoelectricity is opened
The second thermocouple of even summation detects the temperature of the first warm area and the second warm area respectively, and the first warm area and the second warm area are set one respectively
Target temperature, and specify reach the target temperature corresponding heat time, the first heater strip and the second heater strip begin to warm up, with
Temperature is raised, and ampoule interior pressure rises, and sensor body detects quartz diaphragm deformation, and the aobvious system reading of control occurs to become
Change, now by air inlet to filling with inert gas inside pressure vessel so that the aobvious system reading of control returns to initial position, repeats this
Operation, until the first warm area and the second warm area reach target temperature, controls ampoule bottle inside and outside differential pressure and is less than 1atm in whole process,
After temperature reaches target temperature, held for some time, in insulating process, the electron level that gaseous state yellow phosphorus is constantly converted into solid-state is red
Phosphorus, ampoule interior pressure constantly decline, and ampoule bottle external pressure is more than ampoule pressure of the inside of a bottle, and the aobvious system reading of control is to other direction
Change, the inert gas in pressure vessel is discharged by gas outlet according to the change of control aobvious system reading, it is ensured that control is aobvious
System reading returns to original position；After insulation terminates, slowly by the temperature in the first warm area and the second warm area Liang Ge areas by certain
Temperature fall time is down to outlet temperature respectively；
S6：The flange of pressure vessel after reaction terminates, is opened, displacement transducer is removed, ampoule bottle is taken out, is cut off from ampoule bottle
Quartzy pipe cap, takes out electronic grade red phosphorus in bottle.
As a further improvement on the present invention, the S3 is specially ampoule bottle is placed on a welded tube stove and is incited somebody to action using oxyhydrogen flame
Inlet is sealed.
As a further improvement on the present invention, in the S1, quartz ampoule, the cleaning of quartzy pipe cap are specially and use 901 clearing glass
Lotion, deionized water, AR level alcohol are cleaned successively.
As a further improvement on the present invention, in the S5, the target temperature of the first warm area is 470 ~ 510 DEG C, the heat time
For 8 ~ 12h, the target temperature of the second warm area is 430 ~ 470 DEG C, and the heat time is 8 ~ 12h；When the first warm area, the second warm area two
After the temperature of warm area respectively reaches target temperature, 13 ~ 17h is incubated respectively, after insulation terminates, the outlet temperature of the first warm area cooling
For 70 ~ 120 DEG C, the outlet temperature of the second warm area cooling is 40 ~ 70 DEG C, and temperature fall time is controlled in 6 ~ 10h.
The preparation facilities and method of the electronic grade red phosphorus that the present invention is adopted, yellow phosphorus are converted into the process safety of red phosphorus, controllable,
And due to using confined reaction device, the high conversion rate of yellow phosphorus；Using silica ware as reaction vessel, stone at the reaction temperatures
Product electronic grade red phosphorus will not be polluted by the performance quite stable of English vessel, and the purity of gained electronic grade red phosphorus can reach
More than 99.9999%.
Description of the drawings
Fig. 1 is the structural representation of the embodiment of the preparation facilities of electronic grade red phosphorus of the present invention.
Fig. 2 be the preparation facilities of electronic grade red phosphorus of the present invention embodiment in quartzy pipe cap structural representation.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that described enforcement
Example is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention, this area is common
The every other embodiment obtained under the premise of creative work is not made by technical staff, belongs to the model of present invention protection
Enclose.
Device embodiment.
As shown in Figure 1, 2, the preparation facilities 100 of a kind of electronic grade red phosphorus, including pressure vessel 1, heater 2, reaction dress
Put 3 and vavuum pump 4.
Pressure vessel 1 includes the air inlet 11 for inflation, the gas outlet 12 for deflation, the pressure gauge of detection pressure
13rd, for the flange 14 of sealing, support 15 and vessel 16, in the present embodiment, flange 14 includes forward flange and rear method
It is blue.
Heater 2 in pressure vessel 1 includes the first thermocouple 21, the second thermocouple 22,23 and of a heating platform
One controller 24, the first thermocouple 21, the second thermocouple 22 are spaced apart from each other and are embedded in heating platform 23 and fix, heating platform 23
It is fixed on support 15, heating platform 23 includes the first heater strip 231 and the second heater strip 232, controller 24 is controlled for surveying
First thermocouple 21 of temperature, the second thermocouple 22.In certain embodiments of the present invention, heater 2 also includes some heat-preservation cottons
25, heat-preservation cotton 25 is respectively placed in the different parts of ampoule bottle 31 to be used to be incubated.
Be placed on heating platform 23 fixed reaction unit 3 include ampoule bottle 31, quartz diaphragm 32, displacement transducer 33,
Fixture 34, ampoule bottle 31 are formed by connecting by quartz ampoule 311 and quartzy pipe cap 312, as shown in Fig. 2 one end of quartzy pipe cap 312
Including an inlet 313, the other end of quartzy pipe cap 312 is connected one chamber 36 of formation, is prolonged before and after chamber 36 with quartz ampoule 311
Stretch, chamber 36 is divided into reaction chamber 361 and mating cavity 362 by quartz diaphragm 32, displacement transducer 33 includes sensor body 331
With the aobvious system 332 of control, in mating cavity 362 against quartz diaphragm 32, sensor body 331 is by fixture 34 for sensor body 331
Fixed, the aobvious system 332 of control is electrically connected with sensor body 331.
First heater strip 231 and the second heater strip 232 close on quartz diaphragm 32 and reaction chamber 361, the first heater strip respectively
231 and second heater strip 232 form the first warm area and the second warm area in heating platform 23 and ampoule bottle 31 when heating.
For the vavuum pump 4 that pressure vessel 1 is vacuumized, in certain embodiments of the present invention, vavuum pump 4 is held with pressure
Pass through corrugated flexible hose between device 1 and KF joints connect；In certain embodiments of the present invention, vavuum pump 4 is rotary vane mechanical pump.
In certain embodiments of the present invention, the thickness of quartz diaphragm 32 is 2 ~ 4mm, when the pressure reduction of quartz diaphragm both sides is
During 1atm, the shape of quartz diaphragm is changed into 3 ~ 6 μm.
In certain embodiments of the present invention, fixture 34 can be formed using materials processings such as stainless steel, polytetrafluoros.Pressure
The main material of container 1 is stainless steel.First heater strip 231 and the second heater strip 232 are Fe-Cr-Al alloys, and heat-preservation cotton 25 is
Alumina silicate heat-preservation cotton or alumina silicate rigid material；First thermocouple 21, the second thermocouple 22 are K-type thermocouple.Displacement sensing
Device 33 is from essence amount electronics（Shenzhen）Co., Ltd buys, and its range is ± 1000 μm.
The preparation facilities 100 of electronic grade red phosphorus determines the pressure that quartz diaphragm 32 is subject to by displacement transducer 33 is accurate,
By the inside and outside differential pressure for inflating and being vented reaction unit 3 in adjustment pressure vessel 1 so that yellow phosphorus is converted into the process peace of red phosphorus
Entirely, it is controllable.
Embodiment of the method.
A kind of preparation method of electronic grade red phosphorus, using the preparation facilities 100 of above-mentioned electronic grade red phosphorus, including following step
Suddenly：
S1：Quartz ampoule 311, quartzy pipe cap 312 are cleaned up and dried, quartz ampoule 311 and quartzy pipe cap 312 are welded on into one
Rise and form ampoule bottle 31；
S2：Inert gas replacement air is passed through into ampoule bottle 31, after replacing completely, 6N yellow phosphorus is injected by inlet 313
To in ampoule bottle, when yellow phosphorus liquid level is close to inlet 313, stop plus yellow phosphorus；
S3：The inlet 313 of the ampoule bottle 31 equipped with yellow phosphorus is sealed, and during being somebody's turn to do, still indifferent gas is passed through into ampoule bottle 31
Body；
S4：After completing tube sealing, ampoule bottle 31 is put on heating platform 23, fixes the first thermocouple 21 and the second thermocouple 22；
Close the flange 14 of pressure vessel 1, opens vavuum pump 4 and is evacuated to the pressure in pressure vessel 1 less than 1mbar；Using fixture 34
Sensor body 331 is fixed, and completes the abutting of sensor body 331 and quartz diaphragm 32, complete displacement transducer 33
Debugging；
S5：First heater strip 231 and the second heater strip 232 close on quartz diaphragm 32 and reaction chamber 361, the first heater strip respectively
231 and second heater strip 232 form the first warm area and the second warm area in heating platform 23 and ampoule bottle 31 when heating, open control
Device processed 24, the first thermocouple 21 and the second thermocouple 22 detect the temperature of the first warm area and the second warm area respectively, the first warm area and
Second warm area sets a target temperature respectively, and specifies and reach the target temperature corresponding heat time, the first heater strip 231 and the
Two heater strips 232 begin to warm up, and as temperature is raised, 31 internal pressure of ampoule bottle rises, and sensor body 331 detects quartz
Diaphragm 32 deforms, and aobvious 332 reading of system of control changes, now by air inlet 11 to 1 inside filling with inert gas of pressure vessel,
So that aobvious 332 reading of system of control returns to initial position, repeat this operation, until the first warm area and the second warm area reach target temperature
Degree, controls 31 inside and outside differential pressure of ampoule bottle and is less than 1atm in whole process, after temperature reaches target temperature, held for some time,
In insulating process, gaseous state yellow phosphorus is constantly converted into the electronic grade red phosphorus of solid-state, and 31 internal pressure of ampoule bottle constantly declines, ampoule bottle
More than pressure in ampoule bottle 31, aobvious 332 reading of system of control changes 31 external pressures to other direction, according to the aobvious system 332 of control
Inert gas in pressure vessel 1 is discharged by the change of reading by gas outlet 12, it is ensured that aobvious 332 reading of system of control is returned to initially
Position；After insulation terminates, slowly the temperature of the first warm area and the second warm area Liang Ge areas is down to respectively by certain temperature fall time
Outlet temperature；
S6：The flange 14 of pressure vessel 1 after reaction terminates, is opened, displacement transducer 33 is removed, ampoule bottle 31 is taken out, from ampoule
On bottle 31, the quartzy pipe cap 312 of excision, takes out electronic grade red phosphorus in bottle.
During whole reaction, all a little higher than second warm area of warm area of the first warm area, its reason are to ensure quartz
Yellow phosphorus steam near diaphragm 32 will not be condensed into solid yellow phosphorus.
In certain embodiments of the present invention, S3 is specially ampoule bottle 31 is placed on a welded tube stove and will be noted using oxyhydrogen flame
Inlet seal.
In certain embodiments of the present invention, in S1, quartz ampoule 311, the cleaning of quartzy pipe cap 312 are specially and use 901 glass
Cleaning agent, deionized water, AR level alcohol are cleaned successively.
According to said method, following embodiments 1 and embodiment 2 are carried out successively.
6N yellow phosphorus used is by industrial yellow phosphorus through the work such as oxidation arsenic removal, charcoal absorption de- organic matter, chlorination rectifying, reduction
Sequence obtains the yellow phosphorus of more than 6N, and the impurity content in raw material yellow phosphorus is shown in Table 1.
Embodiment 1.
Device is installed according to Fig. 1, quartz ampoule 311 is welded to form an ampoule bottle 31 with quartzy pipe cap 312, by inlet
313 are passed through argon gas（Other inert gases are can use to replace）Air in displacement ampoule bottle 31, argon gas flow velocity 3L/min will after 2 hours
6N（Purity ＞ 99.9999%）Yellow phosphorus is added in ampoule bottle 31, until yellow phosphorus liquid level near 313 lower end of inlet when stop plus
Yellow phosphorus, altogether plus yellow phosphorus 5000g.Inlet 313 is sealed under the protection of argon gas.Then ampoule bottle 31 is attached in heater 2,
Heat-preservation cotton 25, the first thermocouple 21 and the second thermocouple 22 are installed as shown in Figure 1.Sensor body is fixed by fixture 34
331, and the reading of the aobvious system 332 of control is adjusted at 500 μm, with the flange 14 of bolt fastening pressure container 1.Open vavuum pump 4
1 internal pressure of pressure vessel is evacuated to into 0.8mbar.The target temperature of the first warm area is set as 510 DEG C, the heat time is 10h, the
The target temperature of two warm areas is 470 DEG C, and the heat time is 10h；After the temperature of two warm areas reaches target temperature, it is incubated respectively
17h, insulation start cooling after terminating, the final temperature for arranging the first warm area is 120 DEG C, and the final temperature for arranging the second warm area is
70 DEG C, temperature fall time is 10h.
As the temperature of two warm areas rises, in ampoule bottle 31, pressure is continuously increased, and quartz diaphragm 32 is bent outwardly, sensing
Device body 331 is pressurized, and the reading of the aobvious system 332 of control becomes big, when its reading change is more than 4 μm, by air inlet 11 to pressure
Inflated with nitrogen in container 1, until the reading of the aobvious system 332 of control returns to 500 ± 2 μm；Operate more than must repeating in whole process, when two
After the temperature of individual warm area reaches target temperature, now 31 internal pressure of ampoule bottle is 9 atm.In insulation and temperature-fall period, due to
Gaseous yellow phosphorus is converted into solid-state red phosphorus, and in ampoule bottle 31, pressure can be gradually reduced, and now quartz diaphragm 32 curves inwardly, and control is aobvious
The reading of system 332 diminishes, and when its reading change is more than 4 μm, must pass through gas outlet 12 by a part of nitrogen in pressure vessel 1
Gas is discharged, until the reading of the aobvious system 332 of control returns to 500 ± 2 μm, repeats the operation of above bleed, until in pressure vessel 1
Pressure drops to 1 atm, after the temperature of two warm areas reaches outlet temperature, opens the flange 14 of pressure vessel 1, takes out ampoule bottle
31.Ampoule bottle 31 is cut along quartzy 312 afterbody of pipe cap with diamond cutting sawing, the quality of gained red phosphorus is 4516g altogether, is turned
Rate is 90.32%.
The purity of red phosphorus is analyzed using GDMS, the electronic grade red phosphorus that purity can reach more than 99.9999% are obtained, gained into
In product, the content of impurity element is shown in Table 1.
Embodiment 2.
Installing is installed according to Fig. 1 standby, quartz ampoule 311 is welded to form an ampoule bottle 31 with quartzy pipe cap 312, by injection
313 logical argon gas of mouth（Other inert gases are can use to replace）Air in displacement ampoule bottle 31, argon gas flow velocity 3L/min.Will after 2 hours
6N（Purity ＞ 99.9999%）Yellow phosphorus is added in ampoule bottle 31, until yellow phosphorus liquid level near 313 lower end of inlet when stop plus
Yellow phosphorus, altogether plus yellow phosphorus 5000g.Inlet 313 is sealed under the protection of argon gas.Then ampoule bottle 31 is installed to into heater 2
It is interior, heat-preservation cotton 25, the first thermocouple 21 and the second thermocouple 22 are installed as shown in Figure 1.Sensed by 34 fixed displacement of fixture
Device 33, and adjust the reading of the aobvious system 332 of control at 550 μm.With the flange 14 of bolt fastening pressure container 1.Open vavuum pump 4
1 internal pressure of pressure vessel is evacuated to into 1mbar.The target temperature of the first warm area is set in controller 24 as 470 DEG C, during heating
Between be 8h, the target temperature of the second warm area is 430 DEG C, and the heat time is 8h；After the temperature of two warm areas reaches target temperature,
13h is incubated respectively, insulation starts cooling after terminating, the final temperature for arranging the first warm area is 70 DEG C, arranges the second warm area most
Finishing temperature is 40 DEG C, and temperature fall time is 6h.
As the temperature of two warm areas rises, in ampoule bottle 31, pressure is continuously increased, and quartz diaphragm 32 is bent outwardly, sensing
Device body 331 is pressurized, and the reading of the aobvious system 332 of control becomes big, when its reading change is more than 4 μm, by air inlet 11 to pressure
Inflated with nitrogen in container 1, until the reading of the aobvious system 332 of control returns to 550 ± 2 μm；Operate more than must repeating in whole process, when two
After the temperature of individual warm area reaches target temperature, now 31 internal pressure of ampoule bottle is 10atm.In insulation and temperature-fall period, due to
Gaseous yellow phosphorus is converted into solid-state red phosphorus, and in ampoule bottle 31, pressure can be gradually reduced, and now quartz diaphragm 32 curves inwardly, and control is aobvious
The reading of system 332 diminishes, and when its reading change is more than 4 μm, must pass through gas outlet 12 by a part of nitrogen in pressure vessel 1
Gas is discharged, until the reading of the aobvious system 332 of control returns to 550 ± 2 μm, more than repetition exhaust reduced pressure operation, until in pressure vessel 1
Pressure drops to 1 atm, after the temperature of two warm areas reaches outlet temperature, opens the flange 14 of pressure vessel 1, takes out ampoule bottle
31.Ampoule bottle 31 is cut along quartzy 312 afterbody of pipe cap with diamond cutting sawing, take out block red phosphorus, altogether gained red phosphorus
Quality is 4450g, and conversion ratio is 89.00%.
The purity of red phosphorus is analyzed using GDMS, the electronic grade red phosphorus that purity can reach more than 99.9999% are obtained, gained into
In product, the content of impurity element is shown in Table 1.
Raw material and lmpurities constituent content in 1 embodiment 1,2 of table
Compared with prior art, the beneficial effects are mainly as follows following aspect.
1st, using the preparation facilities and method of the present invention, yellow phosphorus is converted into the process safety of red phosphorus, controllable, due to ampoule bottle
Inside and outside differential pressure it is little, so be not in that phosphorous vapor is gone out reaction unit and causes blast, and due to using confined reaction device, carrying
The high conversion ratio of product, the conversion ratio of yellow phosphorus are close to 90%.
2nd, using silica ware as reaction vessel, the performance quite stable of silica ware at the reaction temperatures will not be right
Product electronic grade red phosphorus are polluted, and the purity of gained electronic grade red phosphorus can reach more than 99.9999%.
Although being example purpose, the preferred embodiment of the present invention, the ordinary skill people of this area are had been disclosed for
Member will be various to change, it is realized that disclosed in without departing from by appending claims in the case of scope and spirit of the present invention
It is possible for entering, increasing and replacing.
Claims (10)
1. a kind of preparation facilities of electronic grade red phosphorus, it is characterised in that：Including：
Pressure vessel, the pressure vessel include the air inlet for inflation, the gas outlet for deflation, the pressure of detection pressure
Table, the flange for sealing, support and vessel；
Heater, the heater are located in pressure vessel, and the heater includes that the first thermocouple, the second thermocouple, one add
Hot platform and a controller, first thermocouple, the second thermocouple are spaced apart from each other and are embedded in heating platform and fix, described to add
Hot platform is fixed on support, and the heating platform includes the first heater strip and the second heater strip, and the controller controls to be used for
First thermocouple of thermometric, the second thermocouple；
Reaction unit, the reaction unit be placed on heating platform it is fixed, the reaction unit include ampoule bottle, quartz diaphragm,
Displacement transducer and fixture, the ampoule bottle are formed by connecting by quartz ampoule and quartzy pipe cap, one end of the quartzy pipe cap
Including an inlet, the other end of the quartzy pipe cap is connected to form a chamber with quartz ampoule, extends before and after the chamber, described
Chamber is divided into reaction chamber and mating cavity by quartz diaphragm, and institute's displacement sensors include sensor body and the aobvious system of control, institute
State sensor body to be fixed by fixture, in mating cavity against quartz diaphragm, the control shows system and passes the sensor body
Sensor body is electrically connected with, and first heater strip and the second heater strip close on quartz diaphragm and reaction chamber respectively；
And the vavuum pump vacuumized for pressure vessel.
2. the preparation facilities of electronic grade red phosphorus according to claim 1, it is characterised in that：The heater also include for
Some heat-preservation cottons of ampoule bottle insulation.
3. the preparation facilities of electronic grade red phosphorus according to claim 2, it is characterised in that：The thickness of the quartz diaphragm is
2 ~ 4mm, when the pressure reduction of quartz diaphragm both sides is 1atm, the shape of quartz diaphragm is changed into 3 ~ 6 μm.
4. the preparation facilities of electronic grade red phosphorus according to claim 3, it is characterised in that：The vavuum pump and pressure vessel
Between pass through corrugated flexible hose and KF joints and connect.
5. the preparation facilities of electronic grade red phosphorus according to claim 4, it is characterised in that：The vavuum pump is rotary vane type machine
Tool pump.
6. the preparation facilities of electronic grade red phosphorus according to claim 5, it is characterised in that：First thermocouple and second
Thermocouple is K-type thermocouple.
7. a kind of preparation method of electronic grade red phosphorus, it is characterised in that：Using the arbitrary described electronic grade red phosphorus of claim 1-6
Preparation facilities, comprise the steps：
S1：Quartz ampoule, quartzy pipe cap are cleaned up and dried, quartz ampoule and quartzy pipe cap are welded together to form into ampoule
Bottle；
S2：Inert gas replacement air is passed through into ampoule bottle, after replacing completely, 6N yellow phosphorus ampoule is injected into into by inlet
In bottle, when yellow phosphorus liquid level is close to inlet, stop plus yellow phosphorus；
S3：The inlet sealing of the ampoule bottle equipped with yellow phosphorus, during being somebody's turn to do, still inert gas is passed through into ampoule bottle；
S4：After completing tube sealing, ampoule bottle is put on heating platform, fixes the first thermocouple and the second thermocouple；Close pressure
The flange of container, opens vavuum pump and is evacuated to the pressure in pressure vessel less than 1mbar；It is sensor body is solid using fixture
Determine, and complete the abutting of sensor body and quartz diaphragm, complete the debugging of displacement transducer；
S5：First heater strip and the second heater strip close on quartz diaphragm and reaction chamber, first heater strip and respectively
The first warm area and the second warm area are formed in heating platform and ampoule bottle when two heater strips are heated, controller, the first thermoelectricity is opened
The second thermocouple of even summation detects the temperature of the first warm area and the second warm area respectively, and the first warm area and the second warm area are set one respectively
Target temperature, and specify reach the target temperature corresponding heat time, the first heater strip and the second heater strip begin to warm up, with
Temperature is raised, and ampoule interior pressure rises, and sensor body detects quartz diaphragm deformation, and the aobvious system reading of control occurs to become
Change, now by air inlet to filling with inert gas inside pressure vessel so that the aobvious system reading of control returns to initial position, repeats this
Operation, until the first warm area and the second warm area reach target temperature, controls ampoule bottle inside and outside differential pressure and is less than 1atm in whole process,
After temperature reaches target temperature, held for some time, in insulating process, the electron level that gaseous state yellow phosphorus is constantly converted into solid-state is red
Phosphorus, ampoule interior pressure constantly decline, and ampoule bottle external pressure is more than ampoule pressure of the inside of a bottle, and the aobvious system reading of control is to other direction
Change, the inert gas in pressure vessel is discharged by gas outlet according to the change of control aobvious system reading, it is ensured that control is aobvious
System reading returns to original position；After insulation terminates, slowly by the temperature in the first warm area and the second warm area Liang Ge areas by certain
Temperature fall time is down to outlet temperature respectively；
S6：The flange of pressure vessel after reaction terminates, is opened, displacement transducer is removed, ampoule bottle is taken out, is cut off from ampoule bottle
Quartzy pipe cap, takes out electronic grade red phosphorus in bottle.
8. the preparation method of electronic grade red phosphorus according to claim 7, it is characterised in that：The S3 is specially ampoule bottle
It is placed on a welded tube stove and inlet is sealed using oxyhydrogen flame.
9. the preparation method of electronic grade red phosphorus according to claim 7, it is characterised in that：Quartz ampoule, quartz in the S1
The cleaning of pipe cap is specially and is cleaned with 901 glass cleaners, deionized water, AR level alcohol successively.
10. the preparation method of electronic grade red phosphorus according to claim 7, it is characterised in that：First warm area in the S5
Target temperature is 470 ~ 510 DEG C, and the heat time is 8 ~ 12h, and the target temperature of the second warm area is 430 ~ 470 DEG C, and the heat time is 8
~12h；After the temperature of the first warm area, second two warm areas of warm area respectively reaches target temperature, 13 ~ 17h, insulation are incubated respectively
After end, the outlet temperature of the first warm area cooling is 70 ~ 120 DEG C, and the outlet temperature of the second warm area cooling is 40 ~ 70 DEG C, cooling
Time is controlled in 6 ~ 10h.
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| CN112374474A (en) * | 2020-11-13 | 2021-02-19 | 广东先导先进材料股份有限公司 | Preparation method of compact ultrahigh-purity material |
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