CN105080434B - A kind of catalytic reactor, system, the method for silicon tetrachloride catalytic hydrogenation - Google Patents
A kind of catalytic reactor, system, the method for silicon tetrachloride catalytic hydrogenation Download PDFInfo
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Abstract
The invention discloses a kind of catalytic reactor, system, the method of silicon tetrachloride catalytic hydrogenation, the catalytic reactor includes unstripped gas entrance and product gas outlet, also include sheet material, gas passage one adjacent successively is limited between these sheet materials, catalyst loads passage, gas passage two, gas passage one and catalyst load and are provided with least one first passage on the sheet material between passage, catalyst loads and is provided with least one second passage on the sheet material between passage and gas passage two, unstripped gas carries out unstripped gas distribution using gas passage one or gas passage two, then, unstripped gas after being mounted with the catalyst loading passage of catalyst again in a radial fashion by turning into product gas, enter back into another gas passage, discharge catalytic reactor.Unstripped gas along catalyst to load passage radial through and fully being contacted with catalyst, when catalyst amount is larger, it bears, and rate is uniform, utilization rate is high, and is not easy coking and deactivation, and the life-span greatly prolongs.
Description
Technical field
The invention belongs to producing trichlorosilane by using silicon tetrachloride technical field, and in particular to a kind of catalytic reactor, system, four
The method of silicon chloride catalytic hydrogenation.
Background technology
Polysilicon is the basic material of photovoltaic industry, and the polysilicon in the whole world 75~80% uses improved Siemens
Production, large-scale application of the technique in China have nearly 10 years history, because core technology does not break through yet, often produce one ton
Polysilicon has 16 tons or so of by-produced tetrachlorosilane generation.
The prevailing technology of processing silicon tetrachloride (STC) is both at home and abroad at present：Hot hydrogenation process and cold hydrogenation process, both
Technique is all unsatisfactory.For hot hydrogenation process, its treatment temperature is high, causes high energy consumption；Carbon electrode is heated to product gas
Pollution is produced, transformation efficiency is typically maintained in 20% or so, in addition, (1100~1200 DEG C) heating of high temperature cause electrical equipment input to increase
Greatly, it is higher so as to the cost of output unit trichlorosilane.Most domestic manufacturerss handle silicon tetrachloride from cold hydrogenation process at present,
Although the PROCESS FOR TREATMENT temperature is low (500 DEG C~600 DEG C), it can effectively suppress side reaction (TCS+HCl → STC+H2) occur, but grasp
It is very high to make pressure (15atm.~30atm.), causes runtime investment increase.
In cold hydrogenation process, introduce the catalyst of technical grade purity and metallurgical grade silica flour can cause the product gas of generation
Purity substantially reduces, and causes the investment cost of unstripped gas purification system to increase.In addition, the catalyst chlorine introduced in cold hydrogenation process
Change the cuprous silicon grain surface with gaseous absorbent in cold hydrogenation reactor, when the stannous chloride molecule of silicon grain adsorption reaches
To after certain partial pressure, then by reduction and complicated phase forming process, copper silicide (Cu is produced on silicon grain surfacexSiy) particle from
And loaded catalyst is formed, it is sticky high due to this copper silicide particle, it is easy to cause the silicon in supported catalyst
Lumpd between grain, cause the catalytic efficiency of loaded catalyst to reduce.
As shown in figure 1, at present in cold hydrogenation process, the reaction in catalytic reactor 1 is to carry out in the following manner：Raw material
After gas is sufficiently mixed uniformly, by the unstripped gas entrance 8 of catalytic reactor 1 with axial manner by the catalysis in catalytic reactor 1
Agent bed, unstripped gas generate product gas after chemically reacting, product gas flows to the product gas outlet 9 of catalytic reactor 1.When urging
When agent dosage is larger, there is catalyst and bear that rate is uneven, and utilization rate is not high in this catalytic reactor 1, the superiors' catalyst
The shortcomings of easy coking and deactivation；If increasing the contact area of catalyst and reactant by increasing the internal diameter of catalytic reactor 1,
The problems such as catalyst uneven heating is even, and reaction heat is difficult to export, and reaction temperature is difficult to control again be present.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided one kind catalysis is anti-
Answer device, system, the method for silicon tetrachloride catalytic hydrogenation, during using catalytic reactor in the present invention, unstripped gas with along
Catalyst load passage radial direction mode by, and fully contact with catalyst generate product gas.When catalyst amount is larger,
Catalyst in it bears that rate is uniform, utilization rate is high, and catalyst is not easy coking and deactivation, and the life-span greatly prolongs.
Technical scheme is to provide a kind of catalytic reactor, including unstripped gas entrance used by solving present invention problem
And product gas outlet, in addition to sheet material, limit gas passage one adjacent successively between these sheet materials, catalyst load it is logical
Road, gas passage two, the gas passage one and the catalyst, which load, is provided with least one the on the sheet material between passage
One passage, the catalyst, which loads, is provided with least one second ventilation on the sheet material between passage and the gas passage two
Hole,
Unstripped gas carries out the unstripped gas distribution using the gas passage one or the gas passage two, then, described
Unstripped gas in a radial fashion by turning into product gas after being mounted with the catalyst loading passage of catalyst, enters back into another again
An outer gas passage, discharge catalytic reactor.
Preferably, gas distribution grid is provided with the gas passage one or gas passage two, the gas distribution grid is used
In distribution unstripped gas or product gas.
Preferably, it is anti-in the catalysis to load passage, the gas passage two for the gas passage one, the catalyst
Answer in device and set gradually from outside to inside, the periphery for the gas passage one that the sheet material limits out is the catalytic reactor
Outer wall.
Preferably, the unstripped gas entrance is arranged on the outer of gas passage one and placed, and the product gas outlet is set
Put in the both ends or one end of the gas passage two,
Unstripped gas enters the gas passage one by the unstripped gas entrance, by first passage with the side of radial direction
Formula enters the catalyst loading passage for being mounted with catalyst, is obtained by second passage into the gas passage two
To product gas, the product gas discharges the catalytic reactor by the product gas outlet.
Preferably, the unstripped gas entrance is arranged at the middle part of the peripheral height of the gas passage one, and described
One passage at least two, first passage load the piece between passage along the gas passage one and the catalyst
Be distributed in short transverse on material, from first passage of the unstripped gas entrance from the close-by examples to those far off perforated area by it is small to
Big change.
Preferably, the unstripped gas entrance is arranged on the both ends or one end of the gas passage two, and the product gas goes out
Mouth is arranged on the both ends or one end of the gas passage one or placed outside,
Unstripped gas enters the gas passage two by the unstripped gas entrance, by second passage with the side of radial direction
Formula enters the catalyst loading passage for being mounted with catalyst, is obtained by first passage into the gas passage one
To product gas, the product gas discharges the catalytic reactor by the product gas outlet.
Preferably, second passage at least two, second passage is along the gas passage two and institute
State catalyst and load and be distributed in the short transverse on the sheet material between passage, from the unstripped gas entrance from the close-by examples to those far off described the
The ascending change of perforated area of two passages.
Preferably, the gas passage two is drum-shaped passage.
Preferably, the catalyst loads in passage and is provided with thermocouple.
Preferably, first passage is limiting the sheet material of the catalyst loading passage with second passage
On be symmetrical arranged.
The present invention also provides a kind of catalytic hydrogenation system, including above-mentioned catalytic reactor, heat exchanger, unstripped gas supply
To device, product collector, the catalytic reactor is connected with the heat exchanger, and the heat exchanger connects with the unstripped gas feeder
Connecing, the product collector is connected with the heat exchanger,
The unstripped gas that the product gas of outflow supplies with the unstripped gas feeder in the catalytic reactor is in the heat exchange
Exchanged heat in device, the unstripped gas after heat exchange flows into the catalytic reactor, and the product gas after heat exchange flows into the product
In collector.
Preferably, auxiliary heater, the auxiliary are additionally provided between the catalytic reactor and the heat exchanger
The both ends of heater are connected with the heat exchanger and the catalytic reactor respectively, and the auxiliary heater is used for being changed from described
The unstripped gas of hot device outflow is heated, and the unstripped gas after auxiliary heater heating flows into the catalytic reactor again
It is interior.
The present invention also provides a kind of method of silicon tetrachloride catalytic hydrogenation, and unstripped gas silicon tetrachloride and hydrogen are passed through
Above-mentioned catalytic reactor carries out catalytic hydrogenation and obtains trichlorosilane, and the catalyst in the catalytic reactor loads passage
Inside it is mounted with the catalyst of silicon tetrachloride catalytic hydrogenation.
Preferably, the catalyst is cupro silicon.
Preferably, the cupro silicon includes：22~25wt% copper, 73~76wt% silicon.
Preferably, the particle diameter of the catalyst is 1~5mm.
Preferably, the mol ratio of the hydrogen and the silicon tetrachloride is (1.5:1)~(6:1).
Preferably, flow velocity of the mixed gas of the unstripped gas silicon tetrachloride and hydrogen in the catalytic reactor is
0.05~0.5m/s.
Preferably, the temperature in the catalytic reactor is 300~550 DEG C, and the pressure in the catalytic reactor is
0.4~0.6Mpa, the mixed gas of the unstripped gas silicon tetrachloride and hydrogen is in the catalyst during catalytic hydrogenation
It is 1~10 second to load the holdup time on the catalyst in passage.
When the catalytic reactor in using the present invention carries out catalytic reaction, unstripped gas along catalyst to load passage footpath
To mode by catalyst load passage, and sufficiently with catalyst load passage in catalyst contact generate product gas.
When the catalyst amount that catalyst is loaded in passage is larger, the catalyst in it bears that rate is uniform, utilization rate is high, and catalyst
Coking and deactivation is not easy, the life-span of catalyst greatly prolongs.
The alternative existing situ high pressure of catalytic reactor in the present invention is catalyzed cold hydrogenation reactor, beneficial effect：First,
Pass through the unstripped gas and product gas uniform quality of this catalytic reactor；2nd, due to caused product gas and unstripped gas uniform quality,
So as to substantially reduce the post processing of silicon tetrachloride catalytic hydrogenation tail gas investment；3rd, the catalytic reactor (is less than 550 using low temperature
DEG C) under low pressure (being less than 0.6MPa), in catalyst surface gas-solid catalysis occur for the gaseous mixture of silicon tetrachloride and hydrogen, disappear
The potential safety hazard brought except the cold hydrogenation process of existing high pressure；4th, marketing space is huge.
Brief description of the drawings
Fig. 1 is the front view of catalytic reactor of the prior art；
Fig. 2 is the front view of the catalytic reactor in the embodiment of the present invention 2；
Fig. 3 is the top view of the catalytic reactor in the embodiment of the present invention 2；
Fig. 4 is the front view of the catalytic reactor in the embodiment of the present invention 3
Fig. 5 is the structural representation of the catalytic hydrogenation system in the embodiment of the present invention 4；
Fig. 6 is STC catalytic hydrogenations conversion ratio and the graph of a relation of temperature；
Fig. 7 is the holdup time relation of STC catalytic hydrogenations process and reaction stream.
In figure：1- catalytic reactors；2- gas passages one；3- catalyst loads passage；4- gas passages two；5- first is logical
Stomata；The passages of 6- second；The periphery of 7- gas passages one；8- unstripped gas entrances；9- product gas outlets；10- thermocouples；11-
Catalyst；12- closures；13- sheet materials；14- Catalyst packing mouths；15- heat exchangers；16- unstripped gas feeders；17- products are received
Storage；18- hydrogen-holders；19- silicon tetrachloride storage tanks；20- auxiliary heaters；21- heat control units；22- gas distribution grids.
Embodiment
To make those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings and specific embodiment party
Formula is described in further detail to the present invention.
Embodiment 1
As shown in Figure 2 and Figure 4, the present embodiment provides a kind of catalytic reactor 1, including unstripped gas entrance 8 and product gas go out
Mouth 9, the catalytic reactor 1 also includes sheet material 13, and gas passage 1 adjacent successively, catalysis are limited between these sheet materials 13
Agent loads passage 3, gas passage 24, and the gas passage 1 and the catalyst load to be set on the sheet material 13 between passage 3
At least one first passage 5 is equipped with, the catalyst loads to be set on the sheet material 13 between passage 3 and the gas passage 24
At least one second passage 6 is equipped with,
Unstripped gas carries out the unstripped gas distribution, then, institute using the gas passage 1 or the gas passage 24
State unstripped gas again in a radial fashion by be mounted with catalyst 11 the catalyst load passage 3 after turn into product gas, then
Into another gas passage, catalytic reactor 1 is discharged.
When carrying out catalytic reaction using the catalytic reactor 1 in the present embodiment, unstripped gas is logical to be loaded along catalyst
Road 3 loads passage 3 by catalyst in a radial fashion, and sufficiently loads the catalyst 11 in passage 3 with catalyst and contact
Generate product gas.When catalyst load passage 3 in the dosage of catalyst 11 it is larger when, the catalyst 11 in it bear rate uniformly,
Utilization rate is high, and catalyst 11 is not easy coking and deactivation, and the life-span of catalyst 11 greatly prolongs.
The alternative existing situ high pressure of catalytic reactor 1 in the present embodiment is catalyzed cold hydrogenation reactor, beneficial effect：
First, the unstripped gas and product gas uniform quality of this catalytic reactor 1 are passed through；2nd, due to caused product gas and unstripped gas quality
Unanimously, invested so as to substantially reduce the post processing of silicon tetrachloride catalytic hydrogenation tail gas；3rd, the catalytic reactor 1 is (low using low temperature
In 550 DEG C) under low pressure (being less than 0.6MPa), it is anti-that in catalyst surface gas and solid phase catalyzing occurs for the gaseous mixture of silicon tetrachloride and hydrogen
Should, eliminate the potential safety hazard that the cold hydrogenation process of existing high pressure is brought；4th, marketing space is huge.
Embodiment 2
As shown in Figure 2,3, the present embodiment provides a kind of catalytic reactor 1, including unstripped gas entrance 8 and product gas outlet 9,
The catalytic reactor 1 also includes sheet material 13, and gas passage 1 adjacent successively, catalyst dress are limited between these sheet materials 13
Passage 3, gas passage 24 are carried, the gas passage 1 and the catalyst load to be provided with the sheet material 13 between passage 3
At least one first passage 5, the catalyst loads to be provided with the sheet material 13 between passage 3 and the gas passage 24
At least one second passage 6,
The gas passage 1, the catalyst load passage 3, the gas passage 24 in the catalytic reactor 1
Inside set gradually from outside to inside, the periphery 7 for the gas passage one that the sheet material 13 limits out is the catalytic reactor 1
Outer wall.
When carrying out catalytic reaction using the catalytic reactor 1 in the present embodiment, unstripped gas is logical to be loaded along catalyst
Road 3 loads passage 3 by catalyst in a radial fashion, and the catalyst 11 sufficiently loaded with catalyst in passage 3 is abundant
Contact generation product gas.When the dosage of catalyst 11 that catalyst is loaded in passage 3 is larger, it is equal that the catalyst 11 in it bears rate
It is even, utilization rate is high, and catalyst 11 is not easy coking and deactivation, and the life-span of catalyst 11 greatly prolongs.
Catalyst in the present embodiment loads and is provided with Catalyst packing mouth 14 on passage 3, and in the Catalyst packing mouth
Closure 12 is provided with 14.Closure 12 is opened, is filled when catalyst 11 is encased in into catalyst by Catalyst packing mouth 14
After carrying in passage 3, then cover closure 12.It all be sheet material 13 that catalyst, which loads the madial wall of passage 3 and lateral wall, madial wall and outside
There are the second passage 6 and the first passage 5 on the sheet material 13 of side wall respectively.
Preferably, gas distribution grid 22 is provided with the gas passage 1 or gas passage 24, gas distribution
Be distributed with the wooden partition of plate 22 vent cap be used for be distributed the unstripped gas or product gas uniformly through.
Gas distribution grid 22 is particularly provided with the present embodiment in gas passage 1, the gas distribution grid 22 can be with
So that the first passage 5 that unstripped gas passes through slowly on sheet material 13 again after being uniformly distributed in gas passage 1 is entered and urged
Agent is loaded in passage 3, and catalyst loads the second passage 6 and the first ventilation on the madial wall of passage 3 and outside wall sheet 13
Hole 5 forms the radial passage of product gas and unstripped gas, so that unstripped gas is sufficiently uniformly distributed loads passage 3 with catalyst
The catalyst 11 of interior loading fully contacts, so as to improve catalytic efficiency.
Preferably, the unstripped gas entrance 8 is arranged on the periphery 7 of the gas passage one, the product gas outlet 9
The both ends or one end of the gas passage 24 are arranged on,
Unstripped gas silicon tetrachloride and hydrogen enter the gas passage 1 by the unstripped gas entrance 8, by described first
Passage 5 enters the catalyst loading passage 3 for being mounted with catalyst 11 in a radial fashion, by second passage
6 obtain product gas trichlorosilane and HCl gases into the gas passage 24, and the product gas is discharged by the product gas outlet 9
The catalytic reactor 1.
One end of specific gas passage 24 is provided with the product gas outlet 9 in the present embodiment.
Three unstripped gas entrances 8, unstripped gas tetrachloro are specifically provided with the present embodiment on the periphery 7 of gas passage one
SiClx and hydrogen enter gas passage 1 by these three unstripped gas entrances 8, and unstripped gas silicon tetrachloride and hydrogen can be in gases
Uniformly mixed in passage 1.
Preferably, the unstripped gas entrance 8 is arranged at the middle part of the height of the periphery 7 of the gas passage one, described
First passage 5 at least two, first passage 5 along the gas passage 1 and the catalyst load passage 3 it
Between sheet material 13 on short transverse on be distributed, from the perforate of first passage 5 of the unstripped gas entrance 8 from the close-by examples to those far off
The ascending change of area.Unstripped gas loads logical in gas passage 1 along the gas passage 1 and the catalyst
Pressure in the short transverse on sheet material 13 between road 3 from the unstripped gas entrance 8 from the close-by examples to those far off is descending change,
In order to allow unstrpped gas by the first passage 5 enter catalyst load passage 3 different height at catalyst 11 amount
It is almost identical, thus there is provided the perforated area of first passage 5 from the unstripped gas entrance 8 from the close-by examples to those far off by it is small to
Big change.
When unstripped gas entrance 8 is arranged at the middle part of the height of the periphery 7 of gas passage one, unstripped gas can lead in gas
It is distributed in road 1 from centre to the upper and lower ends of the short transverse of gas passage 1, and distribution speed is fast.Along the gas
Passage 1 and the catalyst load the short transverse on the sheet material 13 between passage 3, when the first passage 5 enters from unstripped gas
When mouth 8 is nearer, the pressure of the unstripped gas near the first passage 5 is bigger, then the perforated area of the first passage 5 is smaller；When
When one passage 5 is more remote from unstripped gas entrance 8, the pressure of the unstripped gas near the first passage 5 is smaller, then the first passage 5
Perforated area it is bigger；The perforated area of first passage 5 is carried out according to the method described above, unstripped gas can be led to by gas
The speed that road 1 enters catalyst loading passage 3 is consistent, so that catalyst loads the catalyst 11 in passage 3
Catalytic efficiency be consistent.
Preferably, the gas passage 24 is drum-shaped passage.When gas passage 24 is drum-shaped passage, in gas
The outside of body passage 24 sets gradually catalyst and loads passage 3, gas passage 1, then the catalytic reactor 1 formed is cylinder
Shape, the cylindrical catalytic reactor 1 is regular shape, is manufactured conveniently.
Preferably, the catalyst loads in passage 3 and is provided with thermocouple 10.Thermocouple 10 is used to monitor in Catalytic Layer
Temperature change, it is ensured that temperature difference in catalyst layer is less than 10 DEG C；Thermocouple 10 should not power supply, its only collecting temperature
Signal.
Preferably, first passage 5 is limiting the catalyst loading passage 3 with second passage 6
It is symmetrical arranged on sheet material 13.First passage 5 is symmetrical arranged with the second passage 6, is advantageous to unstripped gas radial through catalyst
Loading the product gas produced after passage 3, radially discharge catalyst loads passage 3.
Embodiment 3
As shown in figure 4, the present embodiment provides a kind of catalytic reactor 1, including unstripped gas entrance 8 and product gas outlet 9, should
Catalytic reactor 1 also includes sheet material 13, gas passage 1 adjacent successively is limited between these sheet materials 13, catalyst loads
Passage 3, gas passage 24, the gas passage 1 and the catalyst load be provided with the sheet material 13 between passage 3 to
Few first passage 5, the catalyst load be provided with the sheet material 13 between passage 3 and the gas passage 24 to
Few second passage 6,
The gas passage 1, the catalyst load passage 3, the gas passage 24 in the catalytic reactor 1
Inside set gradually from outside to inside, the periphery 7 for the gas passage one that the sheet material 13 limits out is the catalytic reactor 1
Outer wall.
When carrying out catalytic reaction using the catalytic reactor 1 in the present embodiment, unstripped gas is logical to be loaded along catalyst
Road 3 loads passage 3 by catalyst in a radial fashion, and sufficiently loads the catalyst 11 in passage 3 with catalyst and contact
Generate product gas.When catalyst load passage 3 in the dosage of catalyst 11 it is larger when, the catalyst 11 in it bear rate uniformly,
Utilization rate is high, and catalyst 11 is not easy coking and deactivation, and the life-span of catalyst 11 greatly prolongs.
Catalyst in the present embodiment loads and is provided with Catalyst packing mouth 14 on passage 3, and in the Catalyst packing mouth
Closure 12 is provided with 14.Closure 12 is opened, is filled when catalyst 11 is encased in into catalyst by Catalyst packing mouth 14
After carrying in passage 3, then cover closure 12.
Gas distribution grid 22 in the same manner as in Example 2 is particularly provided with the present embodiment in gas passage 1, should
Gas distribution grid 22 can cause product gas to pass through slowly the row of product gas outlet 9 after being uniformly distributed in gas passage 1 again
Go out catalytic reactor 1.
Preferably, the unstripped gas entrance 8 is arranged on the both ends or one end of the gas passage 24, the product gas
Outlet 9 is arranged on the both ends or one end of the gas passage 1 or placed outside,
Unstripped gas enters the gas passage 24 by the unstripped gas entrance 8, enters by second passage 6 and fills
The catalyst for being loaded with catalyst 11 loads passage 3, passes radially through first passage 5 and enters the gas passage 1
Product gas is obtained, the product gas discharges the catalytic reactor 1 by the product gas outlet 9.
Preferably, second passage 6 at least two, second passage 6 along the gas passage 24 with
The catalyst loads to be distributed in the short transverse on the sheet material 13 between passage 3, from the unstripped gas entrance 8 from the close-by examples to those far off
The ascending change of perforated area of second passage 6.
The both ends or one end of gas passage 24 are provided with the unstripped gas entrance 8, along the gas passage 24 and institute
State catalyst and load short transverse on the sheet material 13 between passage 3, when both ends of second passage 6 from gas passage 24 or
When the unstripped gas entrance 8 of one end is nearer, the pressure of the unstripped gas near the second passage 6 is bigger, and this is due to unstripped gas by gas
When the both ends or one end of body passage 24 enter the flowing of gas passage 24, the resistance being subject to the inflow of gas passage 24 is small, and
The resistance flowed into the second passage 6 is small, then the perforated area of the second passage 6 is smaller；When the second passage 6 enters from unstripped gas
When mouth 8 is more remote, the pressure of the unstripped gas near the second passage 6 is smaller, then the perforated area of the first passage 5 is bigger；By
The perforated area of two passages 6 is carried out according to the method described above, and unstripped gas can be caused to enter catalyst dress by gas passage 24
The speed for carrying passage 3 is consistent, so that the catalytic efficiency that catalyst loads the catalyst 11 in passage 3 keeps one
Cause.
One end in the present embodiment specifically using gas passage 24 is provided with unstripped gas entrance 8.
Unstripped gas is in gas passage 24, along between the gas passage 24 and catalyst loading passage 3
Pressure in short transverse on sheet material 13 from the unstripped gas entrance 8 from the close-by examples to those far off is descending change, in order to allow original
The catalytic efficiency for the catalyst 11 that material gas is entered by the second passage 6 at the different height of catalyst loading passage 3 is several
It is identical, so there is provided the perforated area of second passage 6 from the unstripped gas entrance 8 from the close-by examples to those far off is ascending
Change.
Embodiment 4
As shown in figure 5, the present embodiment provides a kind of catalytic hydrogenation system, including above-mentioned catalytic reactor 1, heat exchange
Device 15, unstripped gas feeder 16, product collector 17, the catalytic reactor 1 are connected with the heat exchanger 15, the heat exchanger
15 are connected with the unstripped gas feeder 16, and the product collector 17 is connected with the heat exchanger 15,
The product gas trichlorosilane of outflow and HCl and the unstripped gas feeder 16 supply in the catalytic reactor 1
Unstripped gas silicon tetrachloride and hydrogen exchange heat in the heat exchanger 15, and the unstripped gas after heat exchange flows into the catalytic reactor
1, the product gas after heat exchange is flowed into the product collector 17.Hydrogen is input into unstripped gas by hydrogen-holder 18 to supply
To in device 16, silicon tetrachloride is input in unstripped gas feeder 16 by silicon tetrachloride storage tank 19, so by hydrogen and tetrachloro
SiClx is sufficiently mixed uniformly in unstripped gas feeder 16.
Preferably, auxiliary heater 20 is additionally provided between the catalytic reactor 1 and the heat exchanger 15, it is described
The both ends of auxiliary heater 20 are connected with the heat exchanger 15 and the catalytic reactor 1 respectively, and the auxiliary heater 20 is used
Heated in the unstripped gas to being flowed out from the heat exchanger 15, the unstripped gas after the auxiliary heater 20 heating flows again
Enter in the catalytic reactor 1.
Specifically used heat control unit 21 adjusts the electric current of auxiliary heater 20 in the present embodiment, so as to control heating temperature
Degree.The detector of the heat control unit 21 is arranged on the unstripped gas porch of catalytic reactor 1, is believed according to the temperature of detection
Number, the size of the control heated current of heat control unit 21.
The beneficial effect of catalytic hydrogenation system in the present embodiment：First, existing high-pressure catalytic can be substituted completely
Cold hydrogenation process, the technique not only improve STC conversion ratios, and unstripped gas and product gas uniform quality；2nd, due to caused production
Product gas and unstripped gas uniform quality, it is not required to carry out rectifying to product, only need to slightly evaporates and (directly collect), separate silicon tetrachloride and directly exist
For hydrogenation treatment.The operating pressure of the silicon tetrachloride catalytic hydrogenation device 1 of the present invention is low, and subsequent treatment process is simple, from
And substantially reduce the equipment investment of hydrogenation of silicon tetrachloride process；3rd, the safety that the existing cold hydrogenation process of high-pressure catalytic is brought is eliminated
Hidden danger；4th, marketing space is huge.
Embodiment 5
The present embodiment provides a kind of method of silicon tetrachloride catalytic hydrogenation, and unstripped gas silicon tetrachloride and hydrogen are passed through
Above-mentioned catalytic reactor carries out catalytic hydrogenation and obtains trichlorosilane, and the catalyst in the catalytic reactor loads passage
Inside it is mounted with the catalyst of silicon tetrachloride (STC) catalytic hydrogenation.
Lower silicon tetrachloride hydrodehalogenation reaction (STC+H is described below2→ TCS+HCl) thermodynamic process and catalytic machine
Reason：
Silicon tetrachloride and hydrogen enter in reactor, and free radical SiCl is formed at 500 DEG C2, and produced with HCl, such as
Reaction is (1)：
STC+H2→·SiCl2+HCl ⑴
(1) reaction is the endothermic reaction, activation energy is higher, very slow to a certain extent, is the reaction rate control of non-catalytic process
A step is made, hydrogen content is higher, free radical SiCl caused by the process2Amount is bigger.
As free radical SiCl2After being formed with HCl, which part HCl and free radical SiCl2It is such as anti-with reference to generation TCS
Should (2)：
·SiCl2+HCl→TCS ⑵
Reaction (1)+be (2) our common STC+H2→ TCS+HCl reacts.
A small amount of H in course of reaction2With free radical SiCl2(3) chemical combination generates DCS, such as reaction：
·SiCl2+H2→DCS ⑶
In hot hydrogenation reactor, reaction is (1) relatively slow, causes to react the HCl in the TCS and reaction gas (2) formed
(4) chemical combination forms STC, such as reaction：
TCS+HCl→STC+H2 ⑷
This single step reaction is (4) than reacting (2) more slowly.
In the hot hydrogenation reactors of STC, because no catalyst is present, (1) (1), (2), (3) and (4) slower reaction controls
Whole reaction process.Under thermal equilibrium condition, when temperature is very low (500 DEG C), TCS growing amount is seldom, as shown in Figure 1 (figure
In depict H2Mol ratio with STC is 2:1, H2Mol ratio with STC is 3:1, H2Mol ratio with STC is 4:When 1, STC's
The graph of a relation of the relation of conversion ratio and temperature, STC catalytic hydrogenations conversion ratio and temperature be according to thermodynamics Gibb ' s free energys most
Smallization model is calculated), thus the hot hydrogenations of STC will at high temperature (1100~1200 DEG C) carry out it is more to produce
TCS, but under this elevated temperature condition, also strengthened due to reacting (4) process, cause turning for current each production of polysilicon factory STC
Change efficiency and only maintain 20% or so.
In the prior art, low temperature STC catalytic hydrogenations are by introducing catalyst in reaction system, making the speed of reaction (1)
Reaction is substantially exceeded (4), so that STC conversion ratio improves.
In addition, pass through the STC-H from Fig. 72The holdup time of STC catalytic hydrogenations process and reaction stream in hydro genation system
Kinetics relation can be seen that：The holdup time of reaction stream has a significant impact to STC conversion process, that is to say, that：STC-
H2In hydro genation system, STC maximum conversion rate is by two factor controllings：The holdup time τ of temperature and unstripped gas in reactor.
If holdup time τ increases, conversions of the STC to TCS is moved to the E regions of reaction, and STC conversion ratios reduce；It is when the holdup time
τ0When, the STC conversion ratios in system are maximum.If it is τ that can effectively control holdup time of the unstripped gas in catalytic reactor0Second,
Then go out TCS content highests in the product gas that catalytic reactor obtains.
Pass through the discovery that studies for a long period of time of inventor：Influence vital two factors of STC catalytic hydrogenation conversion ratios：One
It is silicon tetrachloride in rich metal silicide copper silicide (CuxSiy, it is that stannous chloride is formed with particle pasc reaction, and is deposited on silicon
Particulate vector surface, play catalytic action)】(5) and (6) adsorption and intermediate, such as reaction are formed by electron transfer reaction.
n(CuxSiy)+SiCl4→[(CuxSiy)nSiCl2]Cl2 ⑸
[(CuxSiy)nSiCl2]Cl2+H2→(CuxSiy)nSiCl2+2HCl ⑹
The second is intermediate aoxidize addition and be reduced regenerating with reducing agent with hydrogen chloride, such as react (7)
(CuxSiy)nSiCl2+2HCl→n(CuxSiy)+HSiCl3 ⑺
The reaction is the rate-determining step of whole dechlorination hydrogenation, that is to say, that hydrogen chloride and silene intermediate (must reach certain
Amount) addition oxidation reaction be rate-determining step, subsequent TCS is produced, and zero charge silicide occurs, then carries out subsequent circular response.
More more crucial to be exactly, in STC to TCS on-catalytic dechlorination hydrogenation reaction, STC hydride conversion rates are with space
Flow velocity increases and reduced, and in STC to TCS catalysis dechlorination hydrogenation reaction, STC hydride conversion rate is independent of spatial flow
Speed and holdup time (0.5 or 0.025s).
The cold hydrogenation process of STC is to carry out in a fluidized bed reactor used by current domestic polysilicon producer.From chlorine
Change cuprous catalysis agent, absolutely dry stannous chloride is white powder, and it has very strong hygroscopicity, absorbs water during storage
Divide and become light green hydroxy copper chloride [Cu (OH) Cl], become COPPER OXYCHLORIDE 37,5 [Cu after heating2(OH)Cl2], even in high temperature 300
~500 DEG C, the stannous chloride of " gasification " is also with coherent condition [∑ ip (CuiCli), i=1~5] exist, balance each other partial pressure
1.05Pa, because its this characteristic plays delayed-action to the reaction after entering reactor.The chlorine added in fluidized-bed reactor
Change it is cuprous be used as unsupported catalyst, the copper through silicon and/or hydrogen reduction deposits on silicon grain surface, then through copper segregation and silicide
Mutually formation, moreover, the induction period that copper silicide is mutually formed is longer, that is to say, that the silicide on silicon grain surface gradually forms.Ask
Topic is that, because the reaction has strong fuel factor (whole process heat release 95.6KJ/mole), very high reaction heat can cause
Sintering between catalyst particle, the catalyst granules of aggregation cause active reduction, and are difficult to adjust conversion ratio.It is in addition, excessively tiny
Catalyst granules separates from product mixtures can also spend considerable expense and abandoned causes very as waste processing
It is big to waste.
Further, since the microcosmic cementation between catalysed particulate, caused active site is reduced, only by increasing system pressure
Power and new catalytic activity point is produced to realize by constantly adding stannous chloride and silica flour, and the regeneration of catalyst does not obtain
Embody.
Packed tower catalytic reactor is selected in the present embodiment, catalyst is pre-loaded with packed tower catalytic reactor, it is excellent
Choosing, the catalyst is cupro silicon, and controls STC-H2Hydrogenation system optimal conversion parameter (temperature, pressure,
Flow, holdup time) operation, to realize the maximization of STC conversion ratios.
Preferably, the cupro silicon includes：25wt% copper, 73wt% silicon.
Preferably, the particle diameter of the catalyst is 1~5mm.
Preferably, the mol ratio of the hydrogen and the silicon tetrachloride is 1.5:1.
Preferably, flow velocity of the mixed gas of the unstripped gas silicon tetrachloride and hydrogen in the catalytic reactor is
0.1m/s。
Preferably, the temperature in the catalytic reactor is 400 DEG C, and the pressure in the catalytic reactor is
0.5Mpa, the mixed gas of the unstripped gas silicon tetrachloride and hydrogen loads logical in the catalyst during catalytic hydrogenation
The holdup time on catalyst in road is 8 seconds.
The conversion ratio of STC in the present embodiment is 23~25%mole, and the catalytic hydrogenation of the STC in catalytic reactor is anti-
Efficient catalytic, energy-saving purpose should be realized.Solve causes the pollution problem of product gas because adding catalyst and silica flour；
Solve the problems, such as artificially to improve cold hydrogenation system pressure because catalyst activity is low；Solve because catalyst and silica flour caking and
Cause the problem of system fluidisation state is unstable, continuous operation is obstructed with product gas outflow line clogging；Solve because pressure is high and
Caused by unnecessary security hidden trouble.
Embodiment 6
The present embodiment provides a kind of method of silicon tetrachloride catalytic hydrogenation, and unstripped gas silicon tetrachloride and hydrogen are passed through
Above-mentioned catalytic reactor carries out catalytic hydrogenation and obtains trichlorosilane, and the catalyst in the catalytic reactor loads passage
Inside it is mounted with the catalyst of silicon tetrachloride catalytic hydrogenation.
Preferably, the catalyst is cupro silicon.
Preferably, the cupro silicon includes：22wt% copper, 76wt% silicon.
Preferably, the particle diameter of the catalyst is 1~5mm.
Preferably, the mol ratio of the hydrogen and the silicon tetrachloride is 4:1.
Preferably, flow velocity of the mixed gas of the unstripped gas silicon tetrachloride and hydrogen in the catalytic reactor is
0.05m/s。
Preferably, the temperature in the catalytic reactor is 300 DEG C, and the pressure in the catalytic reactor is
0.4Mpa, the mixed gas of the unstripped gas silicon tetrachloride and hydrogen loads logical in the catalyst during catalytic hydrogenation
The holdup time on catalyst in road is 10 seconds.
The conversion ratio of STC in the present embodiment is 20%mole.
As listed in table 1 below the method for the silicon tetrachloride catalytic hydrogenation in the present embodiment in different temperature and
The different conversion ratios of STC under pressure.The high conversion rate of STC in the present embodiment.
STC conversion ratios in the present embodiment of table 1
Embodiment 7
The present embodiment provides a kind of method of silicon tetrachloride catalytic hydrogenation, and unstripped gas silicon tetrachloride and hydrogen are passed through
Above-mentioned catalytic reactor carries out catalytic hydrogenation and obtains trichlorosilane, and the catalyst in the catalytic reactor loads passage
Inside it is mounted with the catalyst of silicon tetrachloride catalytic hydrogenation.
Preferably, the catalyst is cupro silicon.
Preferably, the cupro silicon includes：24wt% copper, 75wt% silicon.
Preferably, the particle diameter of the catalyst is 1~5mm.
Preferably, the mol ratio of the hydrogen and the silicon tetrachloride is 3:1.
Preferably, flow velocity of the mixed gas of the unstripped gas silicon tetrachloride and hydrogen in the catalytic reactor is
0.5m/s。
Preferably, the temperature in the catalytic reactor is 450 DEG C, and the pressure in the catalytic reactor is
0.45Mpa, the mixed gas of the unstripped gas silicon tetrachloride and hydrogen loads in the catalyst during catalytic hydrogenation
The holdup time on catalyst in passage is 4 seconds.
The conversion ratio of STC in the present embodiment is 23%mole.
Embodiment 8
The present embodiment provides a kind of method of silicon tetrachloride catalytic hydrogenation, and unstripped gas silicon tetrachloride and hydrogen are passed through
Above-mentioned catalytic reactor carries out catalytic hydrogenation and obtains trichlorosilane, and the catalyst in the catalytic reactor loads passage
Inside it is mounted with the catalyst of silicon tetrachloride catalytic hydrogenation.
Preferably, the catalyst is cupro silicon.
Preferably, the cupro silicon includes：23wt% copper, 75.5wt% silicon.
Preferably, the particle diameter of the catalyst is 1~5mm.
Preferably, the mol ratio of the hydrogen and the silicon tetrachloride is 6:1.
Preferably, flow velocity of the mixed gas of the unstripped gas silicon tetrachloride and hydrogen in the catalytic reactor is
0.3m/s。
Preferably, the temperature in the catalytic reactor is 500 DEG C, and the pressure in the catalytic reactor is
0.6Mpa, the mixed gas of the unstripped gas silicon tetrachloride and hydrogen loads logical in the catalyst during catalytic hydrogenation
The holdup time on catalyst in road is 1 second.
The conversion ratio of STC in the present embodiment is 26%mole.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, but the invention is not limited in this.For those skilled in the art, the essence of the present invention is not being departed from
In the case of refreshing and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as protection scope of the present invention.
Claims (13)
- A kind of 1. method of silicon tetrachloride catalytic hydrogenation, it is characterised in that by unstripped gas silicon tetrachloride and hydrogen by urging Change reactor progress catalytic hydrogenation and obtain trichlorosilane,The catalytic reactor, including unstripped gas entrance and product gas outlet, in addition to sheet material, limit successively between these sheet materials Adjacent gas passage one, catalyst load passage, gas passage two, and the gas passage one loads passage with the catalyst Between sheet material on be provided with least one first passage, the catalyst is loaded between passage and the gas passage two At least one second passage is provided with sheet material,Unstripped gas carries out the unstripped gas distribution, then, the raw material using the gas passage one or the gas passage two Gas in a radial fashion by turning into product gas after being mounted with the catalyst loading passage of catalyst, enters back into other one again Individual gas passage, discharge catalytic reactor；Catalyst in the catalytic reactor loads the catalyst that silicon tetrachloride catalytic hydrogenation is mounted with passage, described Catalyst is cupro silicon, and the cupro silicon includes：22~25wt% copper, 73~76wt% silicon,Temperature in the catalytic reactor is 300~550 DEG C, and the pressure in the catalytic reactor is 0.4~0.6Mpa, institute The mixed gas of the unstripped gas silicon tetrachloride and hydrogen loads urging in passage in the catalyst when stating catalytic hydrogenation Holdup time in agent is 1~10 second.
- 2. according to the method for claim 1, it is characterised in that be provided with gas in the gas passage one or gas passage two Body distribution grid, the gas distribution grid are used to be distributed unstripped gas or product gas.
- 3. according to the method for claim 1, it is characterised in that the gas passage one, the catalyst load passage, institute State gas passage two to set gradually from outside to inside in the catalytic reactor, the gas passage one that the sheet material limits out Periphery be the catalytic reactor outer wall.
- 4. according to the method for claim 3, it is characterised in that the unstripped gas entrance is arranged on the gas passage one To place outside, the product gas outlet is arranged on the both ends or one end of the gas passage two,Unstripped gas enters the gas passage one by the unstripped gas entrance, enters in a radial fashion by first passage The catalyst for entering to be mounted with catalyst loads passage, is produced by second passage into the gas passage two Product gas, the product gas discharge the catalytic reactor by the product gas outlet.
- 5. according to the method for claim 4, it is characterised in that the unstripped gas entrance is arranged at the gas passage one The middle part of the height of periphery, first passage at least two, first passage is along the gas passage one and institute State catalyst and load and be distributed in the short transverse on the sheet material between passage, from the unstripped gas entrance from the close-by examples to those far off described the The ascending change of perforated area of one passage.
- 6. according to the method for claim 3, it is characterised in that the unstripped gas entrance is arranged on the gas passage two Both ends or one end, the product gas outlet are arranged on the both ends or one end of the gas passage one or placed outside,Unstripped gas enters the gas passage two by the unstripped gas entrance, enters in a radial fashion by second passage The catalyst for entering to be mounted with catalyst loads passage, is produced by first passage into the gas passage one Product gas, the product gas discharge the catalytic reactor by the product gas outlet.
- 7. according to the method for claim 6, it is characterised in that second passage at least two, second ventilation Hole loads along the gas passage two and the catalyst to be distributed in the short transverse on the sheet material between passage, from the original Expect the ascending change of perforated area of second passage of gas entrance from the close-by examples to those far off.
- 8. according to the method described in claim 3~7 any one, it is characterised in that the gas passage two leads to for drum-shaped Road.
- 9. according to the method described in claim 1~7 any one, it is characterised in that the catalyst is loaded in passage and set There is thermocouple.
- 10. according to the method described in claim 1~7 any one, it is characterised in that first passage and described second Passage is symmetrical arranged on the sheet material for limiting the catalyst loading passage.
- 11. the method for silicon tetrachloride catalytic hydrogenation according to claim 1, it is characterised in that the catalyst Particle diameter is 1~5mm.
- 12. the method for silicon tetrachloride catalytic hydrogenation according to claim 1, it is characterised in that the hydrogen and institute The mol ratio for stating silicon tetrachloride is (1.5:1)~(6:1).
- 13. the method for the silicon tetrachloride catalytic hydrogenation according to claim 11 or 12, it is characterised in that the raw material Flow velocity of the mixed gas of gas silicon tetrachloride and hydrogen in the catalytic reactor is 0.05~0.5m/s.
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| US4849206A (en) * | 1986-03-13 | 1989-07-18 | Ammonia Casale S.A. | Process to obtain an optimal gas distribution in catalytic beds for heterogeneous reactions in gaseous phase |
| CN2131600Y (en) * | 1992-06-18 | 1993-05-05 | 中国石油化工总公司 | Low-resistance flow distributor of reactor of ridially fixed bed |
| CN101189245A (en) * | 2005-03-09 | 2008-05-28 | Rec硅公司 | Process for the production of hydrochlorosilanes |
| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3710004A1 (en) * | 1987-03-26 | 1988-10-06 | Uhde Gmbh | DEVICE FOR THE CATALYTIC TREATMENT OF NITROGEN AND HYDROGEN |
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|---|---|---|---|---|
| US4849206A (en) * | 1986-03-13 | 1989-07-18 | Ammonia Casale S.A. | Process to obtain an optimal gas distribution in catalytic beds for heterogeneous reactions in gaseous phase |
| CN2131600Y (en) * | 1992-06-18 | 1993-05-05 | 中国石油化工总公司 | Low-resistance flow distributor of reactor of ridially fixed bed |
| CN101189245A (en) * | 2005-03-09 | 2008-05-28 | Rec硅公司 | Process for the production of hydrochlorosilanes |
| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
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Application publication date: 20151125 Assignee: Xinte silicon based new materials Co.,Ltd. Assignor: XINTE ENERGY Co.,Ltd. Contract record no.: X2023990000586 Denomination of invention: A catalytic reactor, system and method for catalytic hydrogenation of Silicon tetrachloride Granted publication date: 20180227 License type: Common License Record date: 20230605 |
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