CN106957061A - The boron chloride process units and method of a kind of low phosgene content - Google Patents
The boron chloride process units and method of a kind of low phosgene content Download PDFInfo
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- CN106957061A CN106957061A CN201710377619.8A CN201710377619A CN106957061A CN 106957061 A CN106957061 A CN 106957061A CN 201710377619 A CN201710377619 A CN 201710377619A CN 106957061 A CN106957061 A CN 106957061A
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Abstract
A kind of boron chloride process units of low phosgene content, wherein, the outlet of drier is connected with the entrance of vertical response furnace bottom, vertical response stove both sides set peep hole and built-in two groups of fixed double-deck reaction tubes, bilayer reaction outer tube layer is that quartz ampoule, internal layer are graphite annulus with quartz ampoule inscribe, boron carbide particles are filled with graphite annulus, double-deck reaction tube upper end outlet is connected to the entrance of the grey device of resistance simultaneously, the outlet access condenser of the grey device of resistance, access storage tank below condenser, and it is respectively arranged with cooling circulating water in condenser and storage tank；In double-deck reaction tube, boron carbide raw material is excessively loaded, prevent that residual chlorine from overflowing, residual carbon is not directly contacted with quartz ampoule after boron carbide chlorination reaction simultaneously, avoid producing synthesis phosgene raw material, phosgene content is reduced to below 3ppm while silicon tetrachloride, remaining chlorine impurity content is reduced, and then reach the requirement of electron level boron chloride, efficiently, stably, reliably, industrialized production can be achieved in production method.
Description
Technical field
The present invention relates to the boron chloride production dress of technical field of chemical material preparation, more particularly to a kind of low phosgene content
Put and method.
Background technology
Boron chloride is a kind of colourless fuming liquids or gas, and non-combustible, irritant acidic smell meets water decomposition generation
Hydrogen chloride and boric acid, and amount of heat is released, hydrochloric acid and borate are decomposed into alcohol.Having many uses for boron chloride, can be used
Make the basic material of optical fiber and produce diborane, boron fibre, boron powder and produce refractory metal boride titanium diboride
With the raw material of the boron-containing compound such as pyrolytic boron nitride.Simultaneously as the strong lewis acid characteristic of its electron deficient pair, can be used as many
Excellent catalyst in organic reaction, the diffusion that high-purity boron chloride is then mainly used in (silicon) process for fabrication of semiconductor device is mixed
The processes such as miscellaneous, ion implanting, dry etching.In addition, high-purity boron chloride can be additionally used in manufacture solar cell device and high energy
The boron source of BTU values is improved in fuel and propellant.
Preparing the method for boron chloride mainly has two kinds：
B2O3+3C+3Cl2=2BCl3+3CO (1)
B4C+6Cl2=4BCl3+C (2)
Reaction equation (1) increases reaction for heat absorption entropy, though cost of material is low, needs to heat always and is reacted, and power consumption is very big,
And complex technical process and produce substantial amounts of phosgene impurity, reaction equation (2) for the anti-reflection of heat release entropy should, start after reaction, reaction
Thermal discharge is much larger than its reaction barrier, and reaction spontaneous can be carried out, so that the energy is saved, it is now general both at home and abroad all to use reaction equation
(2) boron chloride is prepared.
Reaction equation (2) prepares general using quartz SiO during boron chloride2The reaction tube of material, in its preparation process, by
In chlorination, many impurity, the complete residual chlorine Cl of such as unreacted are also easy to produce2, silicon tetrachloride SiCl4, phosgene COCl2And
Impurity metal ion (Fe, Ni, Cu, K, Na etc.) and air content (N2、O2、CO、CO2Deng), wherein, silicon tetrachloride impurity be
Residual carbon under hot conditions after boron carbide chlorination is produced with the direct haptoreaction of quartz reactor：2Cl2+SiO2+ 2C=
SiCl4+2CO；And phosgene impurity is then to be synthesized under conditions of low temperature and activated carbon catalysis by carbon monoxide and chlorine：CO+Cl2
=COCl2。
In above impurity, all there is larger boiling in residual chlorine, silicon tetrachloride, metal ion, composition of air with boron chloride
Point difference, is removed easily in subsequent rectification and purification technique, and phosgene boiling point (8.2 DEG C) and boron chloride boiling point (12.4 DEG C) phase
Difference is very few, is also difficult to remove even with high tray-number destilling tower, and then needs using a series of complex, expensive purification work
For example many heavily adsorbs of skill process, ultraviolet electromagnetic wave radiation, laser emission etc. could be removed.
The purity of boron chloride has a significant impact to the quality of semiconductor devices, optical fiber and solar cell simultaneously,
If impurity phosgene is acted on silicon, it can generate and impair the impurity such as the carbon and oxygen of semiconductor devices.Have benefited from global electronic industry
Fast development, the demand to boron chloride is increasing, the also more and more higher of the requirement to its purity especially phosgene content；
And existing production technology, the content of phosgene is in more than 10ppm-200ppm, and not reaching electron level boron chloride, (phosgene content will
Seek 0.5-10ppm) requirement.
The content of the invention
Technical problem solved by the invention is the boron chloride process units and method for providing a kind of low phosgene content,
To solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention is realized using following technical scheme：
A kind of boron chloride process units of low phosgene content, including it is the drier filled with calcium chloride granules, vertical anti-
Answer the grey device of stove, resistance, condenser pipe and storage tank；Wherein, the outlet of drier is connected with the entrance of vertical response furnace bottom, vertical response
Two groups of fixed double-deck reaction tubes built in stove, bilayer reaction outer tube layer is that quartz ampoule, internal layer are graphite annulus with quartz ampoule inscribe,
Boron carbide particles are filled with graphite annulus, while double-deck reaction tube upper end outlet is connected to the entrance of the grey device of resistance, going out for grey device are hindered
Access storage tank below mouth access condenser, condenser, and it is respectively arranged with cooling circulating water in condenser and storage tank.
In the present invention, it is provided with flow on the entrance connecting pipe of the outlet of drier and vertical response furnace bottom
Meter.
In the present invention, drier is rustless steel container.
In the present invention, vertical response stove is to be provided with vertical Elema electric furnace, vertical Elema electric furnace
12 Elemas, using three-phase electrical heating, 4 Elemas of being connected per circuitry phase, reaction burner hearth inside dimension is 340 × 500 ×
700mm；Elema specification：Overall length 1000mm, diameter 20mm, 1.8 ohm of resistance；Reacting furnace peak power：18Kw, highest is used
1000 DEG C of temperature；And a peep hole is respectively set in vertical response stove top both sides, for observing the reaction feelings in double-deck reaction tube
Condition, especially observes that boron carbide produces the high-temperature region of exothermic reaction with chlorine；Boron carbide particles filling out in double-deck reaction tube
Loading amount is higher than 100mm above peep hole.
In the present invention, the outer layer quartz ampoule of double-deck reaction tube runs through vertical response furnace body and connect setting is vertical anti-
The water cooled seal system at stove two ends is answered, graphite annulus is inscribed within straight line with quartz ampoule, and graphite annulus superposition overall length is quartz ampoule
The 2/3 of overall length, boron carbide particles are loaded in graphite annulus so that most of quartz ampoule no longer directly carries out face with boron carbide and contacted
(original technique boron carbide directly with quartz ampoule comprehensive engagement), but carry out linear contact lay with graphite annulus；In double-deck reaction tube, outer layer
Quartz ampoule be used as seal, the graphite annulus of internal layer is used as reaction barriers, quartz ampoule specification：Long 1450mm, external diameter 100mm,
Internal diameter 92mm；Graphite annulus specification：External diameter 88mm, internal diameter 72mm, single length 100mm, density is more than 1.6g/cm3。
In the present invention, it is the ash fall utensil with dividing plate with quartzy barrier layer to hinder grey device.
In the present invention, using phosgene generation principle " under conditions of low temperature and activated carbon catalysis by carbon monoxide and
Chlorine is synthesized：CO+Cl2=COCl2", by the synthesis material residual chlorine Cl for controlling phosgene in process of production2And carbon monoxide
CO generation, to solve the technical problem for reducing phosgene impurity, the control of residual chlorine is that requirement chlorine reacts completely in reaction zone
Do not spill over to low-temperature space (under the hot conditions of reaction zone be not likely to produce phosgene reaction)；And the generation of carbon monoxide is controlled, one
It is to avoid reaction generation carbon monoxide when crystal reaction tube is contacted with carbon (generating carbon after boron carbide chlorination reaction) and chlorine under high temperature
“2Cl2+SiO2+ 2C=SiCl4+2CO”；Two be the oxygen and moisture that elimination reaction system is included, it is to avoid oxygen and carbon are at high temperature
The carbon monoxide of generation, while the low temperature that phosgene is produced and activated carbon condition are also avoided, therefore, being prepared using said apparatus low
The boron chloride of phosgene content, is comprised the following steps that：
(1) boron carbide particles are loaded into double-deck reaction tube in advance, then assembly reaction system, then purged instead by nitrogen
System is answered, to replace the air and moisture in reaction system, while vertical reacting furnace is heated up, waste gas drains into tail gas absorption
Tower；
(2) from vertical after chlorine is measured after the anhydrous calcium chloride drying process in drier through flowmeter by certain flow
Formula reaction furnace bottom enters double-deck reaction tube；
(3) after being heated to starting 650~850 DEG C of reaction temperature in vertical response stove, dry chlorine is in vertical response
Heat release chlorination reaction is carried out with boron carbide particles in double-deck reaction tube built in stove, course of reaction is：The chlorine of certain flow from
With the boron carbide particles loaded in advance chlorination reaction occurs for the double-deck reaction tube of vertical response furnace bottom entrance and produces first to put
Thermal response high-temperature region, first exothermic reaction high-temperature region temperature is 1000 DEG C, is carbonized with first exothermic reaction high-temperature region
The consumption of boron particles, this exothermic reaction high-temperature region is progressively moved up；Simultaneously as space and graphite between graphite annulus and quartz ampoule
The permeability of, chlorine itself has small part to be spilled over to graphite annulus upper end, and forms second exothermic reaction height on graphite annulus top
Warm area, two exothermic reaction high-temperature regions are reacted simultaneously, and first exothermic reaction high-temperature region is main reaction region, second heat release
Reaction high-temperature region is side reaction area, and in main reaction region, residual carbon is not directly contacted with quartz ampoule after boron carbide chlorination reaction, quartz
Pipe only presses " 2Cl with the online contact position of graphite annulus2+SiO2+ 2C=SiCl4+ 2CO " reaction principles produce silicon tetrachloride impurity and one
Carbonoxide (synthesis phosgene raw material), due to being linear contact lay, when its yield is significantly less than boron carbide and directly contacted with quartz ampoule face
The amount of generation, and in side reaction area, " 2Cl significantly occurs under side reaction area high temperature for the direct comprehensive engagement quartz ampoule of boron carbide2+
SiO2+ 2C=SiCl4+ 2CO " reaction, but this section of reaction length only accounts for the 1/3 of overall reaction length, it is main with the progress of reaction
Reaction zone is moved from the bottom up, and a reaction zone is finally merged into side reaction area, and reaction high temperature is observed in observation hole site
At once logical chlorine terminating reaction is stopped during area；
(4) boron chloride of reaction generation enters condenser after the grey device barrier sedimentation dust of resistance；
(5) the condensed device of boron chloride is condensed into after liquid is collected as finished product into storage tank.
In the present invention, in step (1), boron carbide particles increase acid cleaning process to remove substantial amounts of metal before filling
Impurity, while reducing the chlorination metal ionic impurity content in product, boron carbide particles granularity is 1~3mm after pickling, and purity is
97%, and boron carbide particles loadings exceed the peep hole top 100mm for being arranged on vertical response stove top both sides, in peep hole
It was observed that stopping logical chlorine reaction during high temperature reaction zone at once, there is enough high temperature cabonization boron to consume so above peep hole
The chlorine of spilling so that chlorine can not overflow reaction high-temperature region, both reduce the possibility for producing phosgene, also reduce product in itself
Residual chlorine impurity content；The window phase that high temperature reaction zone passes through peep hole is about 1 hour, and controllability is very strong, and excessive filling is not
The boron carbide of reaction is recyclable to be recycled.
In the present invention, in step (1), the technological parameter for purging reaction system by nitrogen is：Nitrogen purges pressure
0.1~0.3MPa, nitrogen flow is less than 300m3/ h, purge time 1h, 300 DEG C of furnace temperature, to ensure that drying is anhydrous in reaction system
Anaerobic.
In the present invention, in step (2), anhydrous calcium chloride is graininess, and granularity is 1mm, and purity is more than 96%.
In the present invention, in step (3), if chlorine flowrate is too small, reaction efficiency is low；Chlorine flowrate is excessive, it is possible to make
Fail to have reacted in time into chlorine and overflow high temperature reaction zone, cause to synthesize phosgene risk, meanwhile, residual chlorine is also trichlorine in itself
Change one of boron product major impurity, therefore the technological parameter that with boron carbide particles chlorination reaction occurs for chlorine is：Chlorine flowrate is every
100cm2Reaction cross-section is accumulated, and chlorine flowrate is not more than 1500m3/h。
In the present invention, if air and moisture that reaction system is present, during high temperature, oxygen and boron carbide chlorine in air
Residual carbon reaction generation carbon monoxide after change, causes to synthesize phosgene risk；Equally, exist in reaction system under moisture, high temperature
Also have part oxygen carbon monoxide is synthesized with residual carbon and cause phosgene risk；Meanwhile, the presence of moisture is also easily anti-with boron chloride
Hydrogen chloride and boric acid should be generated, hydrogen chloride is one of product impurity in itself, and boric acid then under pyroreaction fusing volatilization (or rise
China), and in pipeline exit cooling deposition (crystallization), and then blocking pipeline causes reacting system pressure rise to there is explosion danger
Danger, nitrogen heating and blowing process can ensure the smooth of reaction and reduction phosgene and hydrogen chloride impurity risk.
In the present invention, 650~850 DEG C of vertical response stove temperature control is to prevent that chlorine flowrate is excessive because of unexpected disturbances
When, chlorine fails reaction in time and overflows high temperature reaction zone (about 1000 DEG C) completely, then is not less than 650 in non high temperature reaction zone
DEG C furnace temperature environment under, the chlorine of spilling also easily reacts consumption completely with boron carbide, will not be spilled over to low outside vertical response stove
Warm area and produce synthesis phosgene risk or cause residual chlorine impurity；Meanwhile, at a high temperature of more than 650 DEG C of vertical response stove, light
Solid/liquid/gas reactions will not also occur.
In the present invention, due to that can not go what moisture removal and raw material boron carbide contained in itself in raw material and reaction system completely
Boron impurity is aoxidized, in chlorination reaction process, the solid-state dust such as boric acid, boron oxide, carbon dust, metal chloride can be produced.Therefore,
The boron chloride come out from vertical response furnace upper end must be introduced into the grey device of resistance and carry out dedusting, to avoid dust from entering follow-up pipe
Road, valve, storage tank result in blockage and contamination of products.In theory, the barrier layer in grey device is hindered using the absorption such as activated carbon, molecular sieve
Agent preferably, refined product can be adsorbed online, but once has the complete residual chlorine of unreacted and carbon monoxide to overflow high temperature reaction zone
(in-furnace temperature will not produce phosgene reaction more than 650 DEG C), i.e. in resistance after the water cooled seal system cooling of vertical response stove
Grey device is cooled to less than 100 DEG C, if the now adsorption catalyst condition such as active charcoal and molecular sieve, will greatly increase synthesis light
The probability of gas, therefore in the present invention, the grey device of resistance, as barrier layer, can prevent the low temperature active charcoal of phosgene generation completely using quartz plate
Catalytic condition.
Beneficial effect：
(1) present invention is excessively filled using boron carbide, and carries out chlorination reaction by double-deck reaction tube, effectively prevents remnants
The spilling of chlorine has simultaneously obstructed the " 2Cl produced when quartz ampoule is contacted with carbon (generating carbon after boron carbide chlorination reaction) and chlorine2+SiO2+C
=SiCl4+ 2CO " reacts, while silicon tetrachloride, remaining chlorine impurity content is reduced by phosgene content be reduced to 3ppm with
Under, and then reach the requirement of electron level boron chloride；
(2) efficiently, stably, reliably, industrialized production can be achieved in the device and method of present invention production boron chloride.
Brief description of the drawings
Fig. 1 is the structural representation of presently preferred embodiments of the present invention.
Fig. 2 is the double-deck reaction tube structural representation in presently preferred embodiments of the present invention.
Fig. 3 is the double-deck reaction tube inscribe in presently preferred embodiments of the present invention and assembling boron carbide schematic diagram.
Embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are readily apparent from clearly, tie below
Conjunction is specifically illustrating, and the present invention is expanded on further.
Referring to a kind of boron chloride process units of low phosgene content of Fig. 1~3, including it is drier 1, flowmeter 2, vertical
Reacting furnace 3, double-deck reaction tube 4, the grey device 5 of resistance, condenser pipe 6, storage tank 7, peep hole 31, quartz ampoule 41, graphite annulus 42, boron carbide
Grain 43；Wherein, drier 1 is the interior rustless steel container for being filled with calcium chloride granules, and the outlet of drier 1 is accessed through flowmeter 2
The entrance of the bottom of vertical response stove 3, vertical response stove 3 is the vertical Elema electric furnace with peep hole 31, and built-in two groups are consolidated
Fixed pattern bilayer reaction tube 4, the double-deck outer layer of reaction tube 4 is that quartz ampoule 41, internal layer are graphite annulus 42 with the inscribe of quartz ampoule 41, graphite
Be filled with boron carbide particles 43 in ring 42, the double-deck upper end outlet of reaction tube 4 is connected to the entrance of the grey device 5 of resistance, the grey device 5 of resistance be band every
The ash fall utensil of plate and quartzy barrier layer, the outlet access condenser 6 of the grey device 5 of resistance, the lower section of condenser 6 access storage tank 7 is cold
Condenser 6 is low-temperature condition with storage tank 7.
The technological process of production is as follows：
Boron carbide particles 43 are loaded into double-deck reaction tube 4 in advance, and (bottom 2/3 contacts graphite annulus 42, the contact of top 1/3 stone
English pipe 41), loadings are higher than the top 100mm of peep hole 31；After the assembling of question response system, reaction system is purged by nitrogen, with
The air and moisture in reaction system are replaced, while the vertical response stove 3 that heats up, waste gas drains into tail gas absorber, vertical response stove 3
It is warming up to after 650~850 DEG C of reaction temperature of startup, by liquid chlorine vaporization and through the anhydrous calcium chloride CaCl in drier 12At drying
Enter double-deck reaction tube 4 from the bottom of vertical response stove 3 after being measured after reason through flowmeter 2 by certain flow；Dry chlorine is vertical
Heat release chlorination reaction is carried out with boron carbide particles 43 in double-deck reaction tube 4 built in formula reacting furnace 3, course of reaction is：One constant current
Chlorination reaction occurs for the boron carbide particles 43 that the chlorine of amount enters double-deck reaction tube 4 from the bottom of vertical response stove 3 and loaded in advance
And first exothermic reaction high-temperature region (about 1000 DEG C) is produced, with the consumption of this exothermic reaction high-temperature region boron carbide particles 43,
Exothermic reaction high-temperature region is progressively moved up；Simultaneously as the infiltration of space and graphite in itself between graphite annulus 42 and quartz ampoule 41
Property, chlorine has small part to be spilled over to the upper end of graphite annulus 42, and forms second exothermic reaction high-temperature region on the top of graphite annulus 42, the
Two exothermic reaction high-temperature regions are side reaction area, and two reaction zones are reacted simultaneously, based on first exothermic reaction high-temperature region
Reaction zone, in main reaction region, residual carbon is not directly contacted with quartz ampoule 41 after boron carbide chlorination reaction, quartz ampoule 41 only with graphite
Press " 2Cl in the online contact position of ring 422+SiO2+ 2C=SiCl4+ 2CO " reaction principles produce silicon tetrachloride impurity and carbon monoxide,
" 2Cl significantly occurs under side reaction area high temperature for side reaction area, the direct comprehensive engagement quartz ampoule 41 of boron carbide2+SiO2+ 2C=
SiCl4+ 2CO " reaction, but this section of reaction length only accounts for the 1/3 of the double-deck length of reaction tube 4, with the progress of reaction, first
Exothermic reaction high-temperature region is moved from the bottom up, and most latter two exothermic reaction high-temperature region is merged into a reaction zone, in peep hole 31
Position stops logical chlorine terminating reaction when observing reaction high-temperature region；The boron chloride of reaction generation is heavy by the grey barrier of device 5 of resistance
It is condensed into after drop dust into condenser 6 after liquid into low-temperature storage tank 7 and is collected as finished product.
Embodiment 1
Purity 97% after 6kg, pickling, 1~3mm of granularity boron carbide particles 43 are loaded into 2 bilayers of vertical response stove 3
In reaction tube 4 (overall length of graphite annulus 42 accounts for the overall length 2/3 of quartz ampoule 41), the loadings of boron carbide particles 43 about exceed vertical response stove
The 3 top 10mm positions of peep hole 32, the double-deck average effective reaction cross-section of reaction tube 4 product is 100cm2；After assembly reaction system
Vertical response stove 3 is warming up to 300 DEG C, and reaction system (pressure 0.1MPa, flow 100m are purged by nitrogen3/ h) 1 hour, to put
The moisture and air changed in system；Double-deck reaction tube 4 is continuously heating to 650 DEG C, reaches after reaction start-up temperature, liquid chlorine is carried out
Enter anhydrous calcium chloride of the drier 1 through granularity 1mm, purity 96% after vaporization buffering and carry out water removal drying, then from vertical anti-
Answer the lower section of stove 3 to enter double-deck reaction tube 4 and carry out chlorination reaction, chlorine flowrate is 1300m3/h；In chlorine and graphite annulus 42
Boron carbide occurs chlorination reaction and produces first exothermic reaction high-temperature region (about 1000 DEG C of temperature, thickness are about 60mm)；Meanwhile,
A small amount of space and graphite of the chlorine between graphite annulus 42 and quartz ampoule 41 is permeated in itself to be spilled over to the top of graphite annulus 42 and forms the
Two exothermic reaction high-temperature regions, in main reaction region, residual carbon is not directly contacted with quartz ampoule 41 after boron carbide chlorination reaction, to keep away
Exempt from " 2Cl2+SiO2+ 2C=SiCl4+ 2CO " reactions produce silicon tetrachloride impurity and carbon monoxide (synthesis phosgene raw material), and two anti-
Area is answered while being reacted, and is progressively moved up, a reaction zone is finally merged into；The boron trichloride gas of generation are reacted from vertical
The top of reacting furnace 3 enters the grey device 5 of resistance after coming out；Boron chloride after the quartzy barrier layer sedimentation dust of the grey device 5 of resistance is again through cold
Condenser 6 is condensed into inflow storage tank 7 after liquid and collected, and condenser 6 and storage tank 7 are using -10 DEG C of cooling circulating waters；Stay in vertical anti-
The position detection of peep hole 31 of stove 3 is answered to stopping logical chlorine reaction in stove during the reaction high-temperature region of double-deck reaction tube 4, overall reaction and
Acquisition time about 16 hours, obtains the boron chloride finished product about 40kg of water white transparency；Products obtained therefrom impurity content is as shown in table 1,
Wherein phosgene content reaches electronic grade product requirement.
Table 1
| Impurity | Residual chlorine Cl2 | Phosgene COCl2 | Silicon tetrachloride SiCl4 |
| Content ppm (V/V) | ≤3 | 2.7 | 65 |
Embodiment 2
Purity 97% after 6kg, pickling, 1~3mm of granularity boron carbide particles 43 are loaded into 2 bilayers of vertical response stove 3
In reaction tube 4 (overall length of graphite annulus 42 accounts for the overall length 2/3 of quartz ampoule 41), the loadings of boron carbide particles 43 about exceed vertical response stove
Accumulate 100cm in the 3 top 10mm positions of peep hole 31, the double-deck average effective reaction cross-section of reaction tube 42；Stood after assembly reaction system
Formula reacting furnace 3 is warming up to 300 DEG C, and reaction system (pressure 0.2MPa, flow 200m are purged by nitrogen3/ h) 1 hour, to replace
Moisture and air in reaction system；Vertical response stove 3 is continuously heating to 750 DEG C, reaches after reaction start-up temperature, liquid chlorine is entered
Enter anhydrous calcium chloride of the drier 1 through granularity 1mm, purity 96% after row vaporization buffering and carry out water removal drying, then from vertical
The lower section of reacting furnace 3 enters double-deck reaction tube 4 and carries out chlorination reaction, and chlorine flowrate is 1400m3In/h, chlorine and graphite annulus 42
Boron carbide occur chlorination reaction and produce first exothermic reaction high-temperature region (about 1000 DEG C of temperature, thickness are about 60mm)；Together
When, space and graphite of a small amount of chlorine between graphite annulus 42 and quartz ampoule 41 are permeated in itself to be spilled over to the top of graphite annulus 42 and is formed
Second exothermic reaction high-temperature region, in main reaction region, residual carbon is not directly contacted with quartz ampoule 41 after boron carbide chlorination reaction, with
Avoid " 2Cl2+SiO2+ 2C=SiCl4+ 2CO " reactions produce silicon tetrachloride impurity and carbon monoxide (synthesis phosgene raw material), two
Reaction zone is reacted, and progressively move up simultaneously, is finally merged into a reaction zone；The boron trichloride gas of generation are reacted from vertical
The top of formula reacting furnace 3 enters the grey device 5 of resistance after coming out；Boron chloride after the quartzy barrier layer sedimentation dust of the grey device 5 of resistance is passed through again
Condenser 6 is condensed into inflow storage tank 7 after liquid and collected, and condenser 6 and storage tank 7 are using -10 DEG C of cooling circulating waters；Stay in vertical
The position detection of peep hole 31 of reacting furnace 3 reacts to logical chlorine is stopped in stove during the reaction high-temperature region of double-deck reaction tube 4, overall reaction
And acquisition time about 15 hours, obtain the boron chloride finished product about 45kg of water white transparency.The products obtained therefrom impurity content such as institute of table 2
Show, wherein phosgene content reaches electronic grade product requirement.
Table 2
| Impurity | Residual chlorine Cl2 | Phosgene COCl2 | Silicon tetrachloride SiCl4 |
| Content ppm (V/V) | ≤1 | 1.3 | 80 |
Embodiment 3
Purity 97% after 6kg, pickling, 1~3mm of granularity boron carbide particles 43 are loaded into 2 bilayers of vertical response stove 3
In reaction tube 4 (graphite annulus overall length accounts for quartz ampoule overall length 2/3), the loadings of boron carbide particles 43 are about more than vertical response stove 3
Accumulate 100cm in the top 10mm positions of peep hole 31, the double-deck average effective reaction cross-section of reaction tube 42；Assembly reaction system rear vertical type is anti-
Answer stove 3 to be warming up to 300 DEG C, reaction system (pressure 0.3MPa, flow 300m are purged by nitrogen3/ h) 1 hour, to replace reaction
Moisture and air in system；Vertical response stove 3 is continuously heating to 850 DEG C, reaches after reaction start-up temperature, liquid chlorine is carried out into vapour
Change and enter anhydrous calcium chloride progress water removal drying of the drier 1 through granularity 1mm, purity 96% after buffering, then from vertical response
The lower section of stove 3 enters double-deck reaction tube 4 and carries out chlorination reaction, and chlorine flowrate is 1500m3/h；Chlorine and the carbon in graphite annulus 42
Change boron to occur chlorination reaction and produce first exothermic reaction high-temperature region (about 1000 DEG C of temperature, thickness are about 60mm)；Meanwhile, it is few
Space and graphite of the amount chlorine between graphite annulus 42 and quartz ampoule 41 are permeated in itself is spilled over to the top of graphite annulus 42 formation second
Individual exothermic reaction high-temperature region, in main reaction region, residual carbon is not directly contacted with quartz ampoule 41 after boron carbide chlorination reaction, to avoid
“2Cl2+SiO2+ 2C=SiCl4+ 2CO " reactions produce silicon tetrachloride impurity and carbon monoxide (synthesis phosgene raw material), two reactions
Area is reacted, and progressively move up simultaneously, is finally merged into a reaction zone, reacts the boron trichloride gas of generation from vertical anti-
Enter the grey device 5 of resistance after answering the top of stove 3 out；Boron chloride after the quartzy barrier layer sedimentation dust of the grey device 5 of resistance is condensed again
Device 6 is condensed into inflow storage tank 7 after liquid and collected, and condenser 6 and storage tank 7 are using -10 DEG C of cooling circulating waters；Stay in vertical response
The position detection of peep hole 31 of stove 3 reacts to logical chlorine is stopped in stove during the reaction high-temperature region of double-deck reaction tube 4, overall reaction and receipts
About 14 hours collection time, the boron chloride finished product about 48kg of water white transparency is obtained, products obtained therefrom impurity content is as shown in table 3, its
Middle phosgene content reaches electronic grade product requirement.
Table 3
| Impurity | Residual chlorine Cl2 | Phosgene COCl2 | Silicon tetrachloride SiCl4 |
| Content ppm (V/V) | ≤1 | 0.8 | 92 |
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (10)
1. a kind of boron chloride process units of low phosgene content, including the drier filled with calcium chloride granules, vertical response
Stove, the grey device of resistance, condenser pipe and storage tank；Characterized in that, the outlet of drier is connected with the entrance of vertical response furnace bottom, it is vertical
Two groups of fixed double-deck reaction tubes built in reacting furnace, bilayer reaction outer tube layer is that quartz ampoule, internal layer are stone with quartz ampoule inscribe
Boron carbide particles are filled with Mo Huan, graphite annulus, while double-deck reaction tube upper end outlet is connected to the entrance of the grey device of resistance, the grey device of resistance
Outlet access condenser, access storage tank below condenser, and cooling circulating water is respectively arranged with condenser and storage tank.
2. the boron chloride process units of a kind of low phosgene content according to claim 1, it is characterised in that in drier
Outlet and vertical response furnace bottom entrance connecting pipe on be provided with flowmeter.
3. a kind of boron chloride process units of low phosgene content according to claim 1, it is characterised in that vertical response
Stove is vertical Elema electric furnace, is provided with 12 Elemas in vertical Elema electric furnace, using three-phase electrical heating, often
Circuitry phase 4 Elemas of series connection；And a peep hole is respectively set in vertical response stove top both sides, boron carbide particles react in bilayer
Amount of fill in pipe is higher than 100mm above peep hole.
4. a kind of boron chloride process units of low phosgene content according to claim 1, it is characterised in that bilayer reaction
The outer layer quartz ampoule of pipe runs through vertical response furnace body and connect setting is in the water cooled seal system at vertical response stove two ends, graphite
Ring is inscribed within straight line with quartz ampoule, and graphite annulus superposition overall length is the 2/3 of quartz ampoule overall length.
5. the boron chloride process units of a kind of low phosgene content according to claim 1, it is characterised in that hindering grey device is
Ash fall utensil with dividing plate with quartzy barrier layer.
6. a kind of boron chloride production method of low phosgene content, it is characterised in that comprise the following steps that：
(1) boron carbide particles are loaded into double-deck reaction tube in advance, then assembly reaction system, then reaction system is purged by nitrogen
System, to replace the air and moisture in reaction system, while vertical reacting furnace is heated up, waste gas drains into tail gas absorber；
(2) from vertical anti-after chlorine is measured after the anhydrous calcium chloride drying process in drier through flowmeter by certain flow
Furnace bottom is answered to enter double-deck reaction tube；
(3) after being heated to starting 650~850 DEG C of reaction temperature in vertical response stove, dry chlorine is in vertical response stove
Heat release chlorination reaction is carried out with boron carbide particles in the double-deck reaction tube put, course of reaction is：The chlorine of certain flow is from vertical
Reaction furnace bottom enters double-deck reaction tube and the boron carbide particles loaded in advance occur chlorination reaction and first heat release of generation is anti-
High-temperature region is answered, first exothermic reaction high-temperature region temperature is 1000 DEG C, with boron carbide in first exothermic reaction high-temperature region
The consumption of grain, this exothermic reaction high-temperature region is progressively moved up；Simultaneously as space and graphite between graphite annulus and quartz ampoule are in itself
Permeability, chlorine has small part to be spilled over to graphite annulus upper end, and forms second exothermic reaction high-temperature region on graphite annulus top,
Two exothermic reaction high-temperature regions are reacted simultaneously, and first exothermic reaction high-temperature region is main reaction region, second exothermic reaction
High-temperature region is side reaction area, and in main reaction region, residual carbon is not directly contacted with quartz ampoule after boron carbide chlorination reaction, and quartz ampoule is only
" 2Cl is pressed with the online contact position of graphite annulus2+SiO2+ 2C=SiCl4+ 2CO " reaction principles produce synthesis phosgene raw material, due to being line
Contact, synthesis phosgene raw material yield is significantly less than the amount produced when boron carbide is directly contacted with quartz ampoule face, and in side reaction
" 2Cl significantly occurs under side reaction area high temperature for area, the direct comprehensive engagement quartz ampoule of boron carbide2+SiO2+ 2C=SiCl4+2CO”
Reaction, but this section of reaction length only accounts for the 1/3 of overall reaction length, and with the progress of reaction, main reaction region is moved from the bottom up,
A reaction zone is finally merged into side reaction area, logical chlorine termination is stopped when reaction high-temperature region is observed in hole site at once observing
Reaction；
(4) boron chloride of reaction generation enters condenser after the grey device barrier sedimentation dust of resistance；
(5) the condensed device of boron chloride is condensed into after liquid is collected as finished product into storage tank.
7. a kind of boron chloride production method of low phosgene content according to claim 6, it is characterised in that step (1)
In, boron carbide particles are before filling, and increase acid cleaning process is to remove substantial amounts of metal impurities, while reducing the chlorauride in product
Belong to ionic impurity content, boron carbide particles granularity is 1~3mm after pickling, and purity is 97%, and boron carbide particles loadings exceed
It is arranged on 100mm above the peep hole of vertical response stove top both sides.
8. a kind of boron chloride production method of low phosgene content according to claim 6, it is characterised in that step (1)
In, the technological parameter for purging reaction system by nitrogen is：Nitrogen purging pressure is 0.1~0.3MPa, and nitrogen flow is less than
300m3/ h, purge time 1h, 300 DEG C of furnace temperature.
9. a kind of boron chloride production method of low phosgene content according to claim 6, it is characterised in that step (2)
In, anhydrous calcium chloride is graininess, and granularity is 1mm, and purity is more than 96%.
10. a kind of boron chloride production method of low phosgene content according to claim 6, it is characterised in that step (3)
In, the technological parameter that with boron carbide particles chlorination reaction occurs for chlorine is：Chlorine flowrate is per 100cm2Reaction cross-section is accumulated, chlorine
Flow is not more than 1500m3/h。
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| CN108298544A (en) * | 2018-03-27 | 2018-07-20 | 江西瑞合精细化工有限公司 | The floatation retracting device and its recovery method of remaining boron carbide in a kind of halogenation boron production process |
| CN110117015A (en) * | 2019-05-16 | 2019-08-13 | 大连科利德光电子材料有限公司 | The purification devices and method of boron chloride |
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| CN113860338A (en) * | 2021-11-01 | 2021-12-31 | 上海翰军实验设备有限公司 | Preparation and purification device and method for high-purity anhydrous beryllium chloride |
| CN116212771A (en) * | 2023-03-09 | 2023-06-06 | 宁波巨化化工科技有限公司 | Liquid phase single reaction kettle capable of circularly reacting to improve overall yield |
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