CN111072033B - Pretreatment system and method for chlorosilane residual liquid - Google Patents
Pretreatment system and method for chlorosilane residual liquid Download PDFInfo
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Abstract
The invention discloses a pretreatment system and a pretreatment method of chlorosilane residual liquid, wherein the system comprises: the device comprises chlorosilane raffinate equipment, a nitrogen storage tank and a liquid ammonia supply unit, wherein an exhaust area, a reaction area and a feeding area are formed in the chlorosilane raffinate equipment from top to bottom, a filter screen is arranged between the feeding area and the reaction area, the exhaust area is provided with a nitrogen inlet and a tail gas outlet, and the feeding area is provided with a liquid material outlet; the nitrogen storage tank is connected with the nitrogen inlet through a first gas transmission pipeline, and a first valve is arranged on the first gas transmission pipeline; the liquid ammonia supply unit comprises a liquid ammonia storage tank, a gasifier and a pressure reducing valve which are sequentially connected, the pressure reducing valve is connected with the feeding area through a second gas transmission pipeline, and a second valve is arranged on the second gas transmission pipeline. The system can solve the problems of long nitrogen replacement time of the chlorosilane residual liquid, large fume in overhaul operation and large fume in residue treatment of the conventional chlorosilane residual liquid equipment during overhaul.
Description
Technical Field
The invention belongs to the technical field of polysilicon, and particularly relates to a pretreatment system and a pretreatment method of chlorosilane residual liquid.
Background
The improved Siemens method can produce a great amount of silicon tetrachloride as a byproduct in the process of producing the polysilicon. At present, more than 90% of polysilicon enterprises treat byproducts by adopting a silicon tetrachloride cold hydrogenation technology, and convert the byproducts into a raw material trichlorosilane for producing polysilicon. The cold hydrogenation technology of silicon tetrachloride is to react metallurgical grade silicon powder, hydrogen and silicon tetrachloride under the condition of certain temperature and pressure under the action of a catalyst to generate trichlorosilane. Since metallurgical grade silicon powder contains metal impurities, fine silicon powder and metal impurities are introduced into the hydrogenated product (chlorosilane). In the quenching tower or the leaching tower and the subsequent chlorosilane rough distillation process, in order to prevent equipment blockage and remove metal impurities, the fine silicon powder and the metal impurities are discharged from the tower bottom along with silicon tetrachloride liquid, and the discharged solid-liquid mixture is hydrogenated residual liquid. In addition, in the reduction process, besides silicon and SiCl 4 、SiH 2 Cl 2 Si in addition to H2 and HCl etc 2 Cl 6 、Si 2 HCl 5 、Si 2 H 2 Cl 4 、Cl 6 OSi 2 And Si (Si) 3 Cl 8 And the byproduct of the double-silicon and multi-silicon atom compounds is generated, and the boiling point of the double-silicon and multi-silicon atom compounds is higher than that of trichlorosilane and silicon tetrachloride, namely the chlorosilane high-boiling-point compound. The reduction tail gas is recovered by a dry method and purified by rectification, and then SiHCl is obtained 3 、SiCl 4 、SiH 2 Cl 2 The materials such as H2, HCl and the like are returned to the system for recycling, and chlorosilane high-boiling residues, part of silicon tetrachloride and a small amount of amorphous silicon are discharged from the rectifying tower kettleAnd then the discharged material is a solid-liquid mixture, namely the purified residual liquid. The hydrogenated raffinate and the purified raffinate are generally mixed and then treated together, so that the chlorosilane raffinate in the polysilicon industry is obtained. After the liquid chlorosilane in the chlorosilane residual liquid is separated, the residual solid impurities such as fine silicon powder, metal chloride and the like and a small amount of chlorosilane residual on the surface of the solid impurities are chlorosilane residues. Chlorosilane is easy to form HCl acid mist in air, and the reaction formula is SiCl 4 +4H 2 O=H 4 SiO 4 +4HCl。
When the larger chlorosilane residual liquid equipment is overhauled, an equipment manhole is required to be opened, and an overhauling personnel enters the equipment from the manhole to carry out overhauling operation. The existing conventional method is that residual liquid in equipment is poured out as much as possible before maintenance, and then nitrogen is used for replacement, namely, liquid materials are volatilized continuously into the nitrogen to be carried out of the equipment by continuously introducing the nitrogen, when the nitrogen replaced by the equipment has almost no acid mist, the equipment maintenance holes are opened, after air enters the equipment, no obvious acid mist or smell exists, the residual chlorosilane in the equipment is little, maintenance can be carried out, and if the obvious acid mist or smell exists, the maintenance holes are closed, and nitrogen replacement is carried out again until the maintenance requirement is met. The replacement process before equipment overhaul is that liquid materials are volatilized continuously and enter nitrogen and are carried out of the equipment by the nitrogen, so that solid residues still remain in the equipment, and the fine silicon powder in the residues is easy to adsorb chlorosilane, so that the replacement time is long. The replacement operation is aimed at a nitrogen reachable area, if the residue is caked thicker, chlorosilane in the residue cannot be contacted with nitrogen and cannot be carried out, even if the replacement is qualified, after the surface residue is removed in the maintenance process, the residue in the interior contacts with air to react to generate a large amount of smog, so that the maintenance operation cannot be continuously carried out. Meanwhile, part of equipment has dead angles in the overhaul process, the replacement effect is poor, so that the overhaul requirement still cannot be met after long-time replacement, an maintainer can only wear special protective clothing and respirators for overhaul, certain potential safety hazards exist, the overhaul efficiency is low, the long overhaul time is delayed, the overhaul cost is increased, and even normal production is delayed.
Smaller chlorosilane residual liquid equipment such as filters, pumps and the like and residual liquid pipelines are required to be replaced by nitrogen before overhauling, and overhauling personnel open the equipment or the pipeline flange for overhauling after the replacement is qualified. The chlorosilane residual liquid equipment and the residual liquid pipeline are difficult to thoroughly replace when nitrogen is replaced, acid mist is easy to generate when residues contact air in the overhaul process, and the environment of a factory is seriously influenced. Meanwhile, in the process of disposing residues, hydrolysis or alkali liquor is generally used for neutralization, so that the reaction is more severe and the acid mist phenomenon is serious.
Therefore, the operation of the existing chlorosilane residual liquid equipment before overhaul is to be improved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a pretreatment system and method for chlorosilane raffinate, which can solve the problems of long nitrogen replacement time of chlorosilane raffinate, large fume during maintenance and large fume during residue treatment of the existing chlorosilane raffinate equipment.
In one aspect of the invention, the invention provides a pretreatment system for chlorosilane raffinate. According to an embodiment of the invention, the system comprises:
the chlorosilane residual liquid device is internally provided with an exhaust area, a reaction area and a feeding area from top to bottom, a filter screen is arranged between the feeding area and the reaction area, the exhaust area is provided with a nitrogen inlet and a tail gas outlet, and the feeding area is provided with a liquid material outlet;
the nitrogen storage tank is connected with the nitrogen inlet through a first gas transmission pipeline, and a first valve is arranged on the first gas transmission pipeline;
the liquid ammonia supply unit comprises a liquid ammonia storage tank, a gasifier and a pressure reducing valve which are sequentially connected, wherein the pressure reducing valve is connected with the feeding area through a second gas transmission pipeline, and a second valve is arranged on the second gas transmission pipeline.
The pretreatment system of the chlorosilane residual liquid adopts nitrogen to firstly treat the chlorosilane residual liquid in the equipmentIn order to avoid solid particles from being carried out along with the liquid material, a filter screen is arranged at the bottom of the reaction zone and can intercept the solid particles in the residual liquid, then a liquid material outlet valve at the bottom of the feeding zone is closed, nitrogen is continuously introduced from a nitrogen inlet, the residual chlorosilane on the surface of the solid particles is continuously volatilized and enters a tail gas outlet to be discharged from the tail gas, after the tail gas at the tail gas outlet is emptied and has no obvious acid mist phenomenon when being contacted with air, the nitrogen supply is closed, ammonia gas is supplied to the chlorosilane residual liquid equipment through a liquid ammonia supply unit, so that chlorosilane and NH in chlorosilane residues in the chlorosilane residual liquid equipment are caused 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, more heat is released, and the silicon imine Si (NH) generated by the reactions can be obtained 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. Therefore, the method can solve the problems of long nitrogen replacement time of the chlorosilane residual liquid, large fume of overhaul operation and large fume of residue treatment when the traditional chlorosilane residual liquid equipment is overhauled, and has higher environmental protection benefit and economic benefit.
In addition, the pretreatment system of chlorosilane residual liquid according to the above embodiment of the invention can also have the following additional technical features:
in some embodiments of the invention, the pore size of the filter screen is 30-50 microns.
In some embodiments of the invention, the nitrogen storage tank is connected to the feed zone by a third gas line, and a third valve is provided on the third gas line.
In some embodiments of the invention, the system further comprises: and the control unit is connected with the temperature detection device on the chlorosilane residual liquid equipment, the second valve and the third valve.
In some embodiments of the invention, the system further comprises: and the tail gas purifying unit is connected with the tail gas outlet.
In yet another aspect of the invention, the invention provides a method for pretreating chlorosilane raffinate. According to an embodiment of the invention, the method comprises:
(1) Supplying nitrogen to the chlorosilane residual liquid equipment through the first gas transmission pipeline by adopting the nitrogen storage tank so as to perform solid-liquid separation on the chlorosilane residual liquid to obtain liquid materials and solid particles respectively, stopping discharging the liquid materials, and volatilizing the chlorosilane residual on the surface of the solid particles along with the nitrogen into tail gas to obtain chlorosilane residues;
(2) And after the tail gas is exhausted and no obvious acid mist exists, closing the first valve, and adopting the liquid ammonia supply unit to supply ammonia gas to the chlorosilane residual liquid equipment through the second gas pipeline so as to enable the chlorosilane residues to react with the ammonia gas, thereby obtaining a solid reactant containing silicon imine, ammonium chloride and metal complex.
According to the pretreatment method of the chlorosilane raffinate, the liquid material in the chlorosilane raffinate equipment is firstly extruded from the bottom of the equipment by adopting nitrogen, a filter screen is arranged at the bottom of a reaction zone to prevent solid particles from being carried out along with the liquid material, the solid particles in the raffinate can be intercepted, then a liquid material outlet valve at the bottom of a feeding zone is closed, and the liquid material is fed from the nitrogenContinuously introducing nitrogen into the port, continuously volatilizing residual chlorosilane on the surface of solid particles, allowing the residual chlorosilane to enter the nitrogen and be discharged from the tail gas outlet, closing the nitrogen supply after the tail gas at the tail gas outlet is emptied and has no obvious acid mist phenomenon when the tail gas contacts with air, and supplying ammonia gas into the chlorosilane residual liquid equipment through the liquid ammonia supply unit, so that chlorosilane and NH in chlorosilane residues in the chlorosilane residual liquid equipment 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, more heat is released, and the silicon imine Si (NH) generated by the reactions can be obtained 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. Therefore, the method can solve the problems of long nitrogen replacement time of the chlorosilane residual liquid, large fume of overhaul operation and large fume of residue treatment when the traditional chlorosilane residual liquid equipment is overhauled, and has higher environmental protection benefit and economic benefit.
In addition, the pretreatment method of the chlorosilane residual liquid according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the present invention, the ammonia pressure after passing through the pressure reducing valve of the liquid ammonia supply unit is 2 to 3bar.
In some embodiments of the invention, the above method further comprises: (3) The temperature of the chlorosilane residual liquid equipment is higher than 300 ℃, and nitrogen is supplied to the feeding area through the third gas transmission pipeline by utilizing the nitrogen storage tank.
In some embodiments of the invention, step (3) further comprises controlling the opening of the second valve and the third valve with the control unit based on a display of a temperature detection device on the chlorosilane raffinate plant.
In some embodiments of the invention, the exhaust gas is supplied to the exhaust gas purification unit for purification treatment.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of a pretreatment system for chlorosilane residues according to one embodiment of the invention;
FIG. 2 is a schematic diagram of a pretreatment system for chlorosilane residues according to a further embodiment of the invention;
FIG. 3 is a schematic diagram of a pretreatment system for chlorosilane residues according to yet another embodiment of the invention;
FIG. 4 is a schematic flow diagram of a method for pretreating chlorosilane residual in accordance with one embodiment of the invention;
FIG. 5 is a schematic flow chart of a pretreatment process for chlorosilane residues according to a further embodiment of the invention;
FIG. 6 is a schematic flow chart of a pretreatment method of chlorosilane residual liquid according to another embodiment of the invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In one aspect of the invention, the invention provides a pretreatment system for chlorosilane raffinate. Referring to fig. 1-3, in accordance with an embodiment of the present invention, the system includes: a chlorosilane residual liquid apparatus 100, a nitrogen tank 200, and a liquid ammonia supply unit 300.
According to the embodiment of the invention, a gas discharge zone 11, a reaction zone 12 and a feeding zone 13 are formed in the chlorosilane residual liquid equipment 100 from top to bottom, a filter screen 14 is arranged between the feeding zone 13 and the reaction zone 12, the gas discharge zone 11 is provided with a nitrogen inlet 101 and a tail gas outlet 102, and the feeding zone 13 is provided with a liquid material outlet 103. Specifically, the pore diameter of the filter screen 14 is 30-50 micrometers (the pore diameter of the filter screen is too large, solid particles cannot be effectively intercepted, the pore diameter is too small, the filter screen is easy to block, and the fluid resistance is large), so that the solid-liquid separation efficiency can be improved, meanwhile, the blocking of the filter screen 14 is avoided, the chlorosilane raffinate in the chlorosilane raffinate equipment 100 is pressurized by supplying nitrogen from the exhaust area 11 to filter the chlorosilane raffinate through the filter screen 14, most of liquid material is extruded from a liquid material outlet 103 at the bottom of the equipment, then a valve at the liquid material outlet 103 is closed, nitrogen is continuously introduced through a nitrogen inlet 101, chlorosilane remained on the surfaces of the solid particles intercepted on the filter screen 14 is continuously volatilized into the nitrogen and is discharged from a tail gas outlet 102, and the remained chlorosilane residue stays in a reaction area 12 above the filter screen 14, and the main components of the chlorosilane residue are as follows: small amount of chlorosilane (mainly silicon tetrachloride), fine silicon powder, and metal chlorides of aluminum, titanium, iron, etc. It should be noted that, the "chlorosilane residual liquid apparatus 100" in the present application is an apparatus conventionally used in the polysilicon production process, and will not be described herein.
According to the embodiment of the invention, the nitrogen storage tank 200 is connected with the nitrogen inlet 101 through the first gas pipeline 21, the first gas pipeline 21 is provided with the first valve 211, namely, the nitrogen in the nitrogen storage tank 200 is continuously supplied into the chlorosilane residual liquid equipment 100 through the first gas pipeline 21 to replace the interior of the chlorosilane residual liquid equipment, and after the tail gas after replacement is exhausted through the tail gas outlet 102 and is in contact with air, no obvious acid mist phenomenon exists, namely, the replacement is completed, and the first valve 211 is closed. Specifically, if chlorosilane is contained in the tail gas, the chlorosilane is extremely easy to react with water in the air to obtain hydrochloric acid so as to form acid mist. It should be noted that "no obvious acid mist phenomenon" in the present application is understood as that no acid mist formation can be observed by naked eyes, and those skilled in the art can distinguish from each other empirically.
According to an embodiment of the present invention, the liquid ammonia supply unit 300 includes a liquid ammonia storage tank 31, a vaporizer 32, and a pressure reducing valve 33 connected in this order, the pressure reducing valve 33 is connected to the feed region 13 through a second gas delivery pipe 34, and a second valve 341 is provided on the second gas delivery pipe 34. Specifically, after the above nitrogen replacement is completed, the liquid ammonia stored in the liquid ammonia storage tank 31 is heated by the vaporizer 32, vaporized into ammonia gas, depressurized by the depressurization valve 33, controlled to have a pressure of 2-3 bar, and then supplied from the feeding area 13 to the chlorosilane residual liquid device 100 through the second gas pipeline 34 to react with chlorosilane residues in the chlorosilane residual liquid device 100, so that chlorosilane and NH in the chlorosilane residues in the chlorosilane residual liquid device 100 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, and more heat is released, and silicon is generated by the reactionsImine Si (NH) 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. Meanwhile, when the ammonia gas is supplied to the chlorosilane residual liquid equipment to replace nitrogen, the tail gas outlet valve is kept closed or slightly opened, so that the ammonia gas is saved.
According to the pretreatment system for the chlorosilane residual liquid, disclosed by the embodiment of the invention, the liquid material in the chlorosilane residual liquid equipment is firstly extruded from the bottom of the equipment by adopting nitrogen, in order to prevent solid particles from being carried out along with the liquid material, a filter screen is arranged at the bottom of a reaction zone and can intercept the solid particles in the residual liquid, then a liquid material outlet valve at the bottom of a feeding zone is closed, the nitrogen is continuously introduced from a nitrogen inlet, the residual chlorosilane on the surface of the solid particles is continuously volatilized and enters a tail gas outlet to be discharged from the tail gas outlet, after the tail gas at the tail gas outlet is emptied and has no obvious acid mist phenomenon in contact with air, the nitrogen supply is closed, ammonia gas is supplied to the chlorosilane residual liquid equipment through a liquid ammonia supply unit, so that chlorosilane and NH in chlorosilane residues in the chlorosilane residual liquid equipment are supplied 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, and more heat is released, and the silicon imine generated by the reactionsSi(NH) 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. Therefore, the method can solve the problems of long nitrogen replacement time of the chlorosilane residual liquid, large fume of overhaul operation and large fume of residue treatment when the traditional chlorosilane residual liquid equipment is overhauled, and has higher environmental protection benefit and economic benefit.
Further, referring to fig. 2, the nitrogen tank 200 is connected to the feeding zone 13 through a third gas transmission pipe 22, and a third valve 221 is provided on the third gas transmission pipe 22. Specifically, as the ammonia gas is supplied to the chlorosilane residual apparatus 100, the nitrogen gas in the chlorosilane residual apparatus 100 is gradually replaced by the ammonia gas and discharged from the tail gas outlet 102, and as the ammonia gas concentration in the chlorosilane residual apparatus 100 increases, the reaction is gradually accelerated, so that the temperature in the chlorosilane residual apparatus 100 increases rapidly, the temperature of the sidewall of the chlorosilane residual apparatus 100 is detected in real time by disposing the temperature detecting device 15 on the sidewall of the reaction zone 12 of the chlorosilane residual apparatus 100, for example, the temperature detecting device 15 is a temperature gun, and when the temperature of the temperature gun to be detected is higher than 300 ℃, the third valve 221 is opened to supply the nitrogen gas into the feed zone 13 to reduce the ammonia gas concentration in the chlorosilane residual apparatus 100, thereby reducing the reaction rate, so as to achieve the purpose of reducing the temperature in the chlorosilane residual apparatus 100. The volume and/or flow rate of the nitrogen gas supplied during this step is based on the fact that the temperature detecting device 15 on the chlorosilane residual apparatus 100 shows a temperature lower than 300 ℃. Preferably, the automation of the system of the present application may be improved by providing a control unit 400, which control unit 400 is connected to the temperature detecting means 15 and the second valve 341 and the third valve 221 on the chlorosilane raffinate installation 100, and is adapted to automatically adjust the opening of the second valve 341 and the third valve 221 based on the temperature display of the temperature detecting means 15, e.g. when the temperature detecting means 15 shows a temperature higher than 300 degrees celsius, the control unit 400 automatically controls the opening of the third valve 221 and/or reduces the opening of the second valve 221. It should be noted that, the control unit 400 is a control device that is conventional in the art, so long as the above functions can be achieved, and the structure thereof will not be described herein.
Further, referring to fig. 3, the above system further comprises an exhaust gas purifying unit 500, which exhaust gas purifying unit 500 is connected to the exhaust gas outlet 102 and adapted to supply an exhaust gas containing a small amount of ammonia gas into the exhaust gas purifying unit 500 after the ammonia gas is supplied to the chlorosilane residual apparatus to complete the replacement of the nitrogen gas. It should be noted that, a person skilled in the art may select the type of the exhaust gas purifying unit 500 according to actual needs, so long as the exhaust gas can reach the standard and be discharged, and the structure thereof will not be described herein.
Further, in the process of supplying ammonia gas to the feeding zone 13 through the second gas pipe 34, if the temperature detecting device 15 on the chlorosilane residual liquid apparatus 100 shows a gradual decrease, that is, the chlorosilane and the metal chloride in the chlorosilane residual liquid apparatus 100 have basically reacted completely, the second valve 341 and the third valve 221 are closed, if the pressure gauge on the chlorosilane residual liquid apparatus is stable, the reaction can be confirmed to be complete, and then the first valve 211 is opened to introduce nitrogen gas to replace the ammonia gas in the chlorosilane residual liquid apparatus 100 completely, so that the chlorosilane residual liquid apparatus 100 can be overhauled.
In a third aspect of the invention, the invention provides a pretreatment method for implementing chlorosilane residual liquid by adopting the system. Referring to fig. 4-6, in accordance with an embodiment of the present invention, the method includes:
s100: nitrogen is supplied to chlorosilane residual liquid equipment through a first gas transmission pipeline by adopting a nitrogen storage tank
In the step, nitrogen is supplied to chlorosilane residual liquid equipment through a first gas transmission pipeline by adopting a nitrogen storage tank so as to carry out solid-liquid separation on the chlorosilane residual liquid, and liquid material, chlorosilane residues and tail gas are respectively obtained. Specifically, the chlorosilane residual liquid in the chlorosilane residual liquid equipment 100 is filtered through a filter screen 14 by supplying nitrogen from an exhaust area 11 to pressurize the chlorosilane residual liquid equipment 100, so that most of liquid material is pressed out from a liquid material outlet 103 at the bottom of the equipment, then a valve at the liquid material outlet 103 is closed, nitrogen is continuously introduced through a nitrogen inlet 101, the chlorosilane residual on the surface of solid particles on the filter screen 14 is blocked from continuously volatilizing into the nitrogen and is discharged from a tail gas outlet 102, and the residual chlorosilane residues remain in a reaction area 12 above the filter screen 14, wherein the main components of the chlorosilane residues are as follows: small amount of chlorosilane (mainly silicon tetrachloride), fine silicon powder, and metal chlorides of aluminum, titanium, iron, etc. It should be noted that, the "chlorosilane residual liquid apparatus 100" in the present application is an apparatus conventionally used in the polysilicon production process, and will not be described herein.
S200: after the tail gas is emptied and no obvious acid mist exists, the first valve is closed, and the liquid ammonia supply unit is adopted to supply ammonia gas into the chlorosilane residual liquid equipment through the second gas transmission pipeline
In this step, after the exhaust gas is exhausted without obvious acid mist, the first valve 211 is closed, and ammonia gas is supplied to the chlorosilane residual liquid apparatus 100 through the second gas transmission line 34 by using the liquid ammonia supply unit 300, so that the chlorosilane residue reacts with the ammonia gas to obtain a solid reactant containing silicon imine, ammonium chloride and a metal complex. Specifically, if chlorosilane is contained in the tail gas, the chlorosilane and air are extremely easy to react with water in the air to obtain hydrochloric acid so as to form acid mist. After the nitrogen replacement is completed, the liquid ammonia stored in the liquid ammonia storage tank 31 is heated by the gasifier 32, gasified into ammonia gas, decompressed by the decompression valve 33, controlled to be 2-3 bar in pressure, and then supplied to the chlorosilane residual liquid equipment 100 from the feeding area 13 through the second gas pipeline 34 to react with chlorosilane residues in the chlorosilane residual liquid equipment 100, so that chlorosilane and NH in the chlorosilane residues in the chlorosilane residual liquid equipment 100 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, more heat is released, and the silicon imine Si (NH) generated by the reactions can be obtained 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. It should be noted that "no obvious acid mist phenomenon" in the present application is understood as that no acid mist formation can be observed by naked eyes, and those skilled in the art can distinguish from each other empirically. Meanwhile, when the ammonia gas is supplied to the chlorosilane residual liquid equipment to replace nitrogen, the tail gas outlet valve is kept closed or slightly opened, so that the ammonia gas is saved.
According to the pretreatment method of the chlorosilane raffinate, the liquid material in the chlorosilane raffinate equipment is firstly extruded from the bottom of the equipment by adopting nitrogen, a filter screen is arranged at the bottom of a reaction zone to prevent solid particles from being carried out along with the liquid material, the solid particles in the raffinate can be intercepted, then a liquid material outlet valve at the bottom of a feeding zone is closed, the nitrogen is continuously introduced from a nitrogen inlet, the residual chlorosilane on the surface of the solid particles is continuously volatilized and enters a tail gas outlet to be discharged from the tail gas outlet, after the tail gas at the tail gas outlet is emptied and is in contact with air, no obvious acid mist phenomenon exists, the nitrogen supply is closed, ammonia gas is supplied to the chlorosilane raffinate equipment through a liquid ammonia supply unit, and the chlorosilane in the chlorosilane residue in the chlorosilane raffinate equipment is causedWith NH 3 (liquid/gas) reaction to give silicon imine Si (NH) 2 The general chemical reaction equation is:
wherein x is the degree of polymerization of the siliconized imine and the metal chloride impurities in the chlorosilane residue are combined with NH 3 The (liquid/gas) reaction produces a complex of metal chloride, the general chemical reaction equation of which is: />
Wherein Me is aluminum, titanium, iron, etc., the two reactions can be carried out at normal temperature and normal pressure, more heat is released, and the silicon imine Si (NH) generated by the reactions can be obtained 2 The ammonium chloride and the metal complex are solid matters and are stable in air, so that the pressure in the reaction process is not increased, the overpressure risk is avoided, compared with the replacement technology before overhaul of the traditional chlorosilane residual liquid equipment, the method does not need to thoroughly replace chlorosilane in the chlorosilane residual liquid, the nitrogen replacement time is greatly shortened, the generated silicon imine, ammonium chloride and metal complex react mildly when meeting water or acid and alkali, no acid mist is generated, and the solid after reaction in the chlorosilane residual liquid equipment can be removed by hydrolysis or acid and alkali neutralization. Therefore, the method can solve the problems of long nitrogen replacement time of the chlorosilane residual liquid, large fume of overhaul operation and large fume of residue treatment when the traditional chlorosilane residual liquid equipment is overhauled, and has higher environmental protection benefit and economic benefit.
Further, referring to fig. 5, the method further includes
S300: the temperature of chlorosilane residual liquid equipment is higher than 300 ℃, and nitrogen is supplied to a feeding area through a third gas transmission pipeline by utilizing a nitrogen storage tank
In this step, specifically, as the above ammonia gas is supplied to the chlorosilane residual apparatus 100, the nitrogen gas in the chlorosilane residual apparatus 100 is gradually replaced by the ammonia gas and discharged from the exhaust gas outlet 102, and as the ammonia gas concentration in the chlorosilane residual apparatus 100 increases, the reaction is gradually accelerated, so that the temperature in the chlorosilane residual apparatus 100 increases rapidly, and by disposing the temperature detecting device 15 on the chlorosilane residual apparatus 100, for example, the temperature detecting device 15 is a temperature measuring gun disposed on the sidewall of the chlorosilane residual apparatus 100, the temperature of the sidewall of the chlorosilane residual apparatus 100 is detected in real time, and when the temperature of the temperature measuring gun is higher than 300 ℃, the third valve 221 is opened to supply the nitrogen gas into the feed zone 13 to reduce the ammonia gas concentration in the chlorosilane residual apparatus 100, thereby reducing the reaction rate and achieving the purpose of reducing the temperature in the chlorosilane residual apparatus 100. Preferably, in this step, the automation of the system of the present application may be improved by providing a control unit 400, which control unit 400 is connected to the temperature detecting means 15 and the second and third valves 341 and 221 on the chlorosilane residual apparatus 100, and is adapted to automatically adjust the opening of the second and third valves 341 and 221 based on the temperature display of the temperature detecting means 15, e.g. when the temperature detecting means 15 displays a temperature higher than 300 degrees celsius, the control unit 400 automatically controls the opening of the third valve 221 and/or reduces the opening of the second valve 221.
Further, referring to fig. 6, the method further includes:
s400: the tail gas is supplied to a tail gas purifying unit for purifying treatment
In this step, after the ammonia gas is supplied to the chlorosilane residual apparatus in the above step S200 to complete the replacement of the nitrogen gas, the off-gas containing a small amount of ammonia gas is supplied to the off-gas purification unit 500.
Further, in the process of supplying ammonia gas to the feeding zone 13 through the second gas pipe 34, if the temperature detecting device 15 on the chlorosilane residual liquid apparatus 100 shows a gradual decrease, that is, the chlorosilane and the metal chloride in the chlorosilane residual liquid apparatus 100 have basically reacted completely, the second valve 341 and the third valve 221 are closed, if the pressure gauge on the chlorosilane residual liquid apparatus is stable, the reaction can be confirmed to be complete, and then the first valve 211 is opened to introduce nitrogen gas to replace the ammonia gas in the chlorosilane residual liquid apparatus 100 completely, so that the chlorosilane residual liquid apparatus 100 can be overhauled.
It should be noted that the features and advantages described in the above pretreatment system for chlorosilane residual liquid are also applicable to the pretreatment method of chlorosilane residual liquid, and are not described herein.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (8)
1. A pretreatment system for chlorosilane residue, comprising:
the chlorosilane residual liquid device is internally provided with an exhaust area, a reaction area and a feeding area from top to bottom, a filter screen is arranged between the feeding area and the reaction area, the exhaust area is provided with a nitrogen inlet and a tail gas outlet, and the feeding area is provided with a liquid material outlet;
the nitrogen storage tank is connected with the nitrogen inlet through a first gas transmission pipeline, and a first valve is arranged on the first gas transmission pipeline;
the liquid ammonia supply unit comprises a liquid ammonia storage tank, a gasifier and a pressure reducing valve which are sequentially connected, the pressure reducing valve is connected with the feeding area through a second gas transmission pipeline, and a second valve is arranged on the second gas transmission pipeline;
the nitrogen storage tank is connected with the feeding area through a third gas transmission pipeline, and a third valve is arranged on the third gas transmission pipeline;
the control unit is connected with a temperature detection device on the chlorosilane residual liquid equipment, the second valve and the third valve, the temperature detection device is a temperature measuring gun, and the temperature measuring gun is arranged on the side wall of the reaction zone.
2. The system of claim 1, wherein the mesh size of the screen is 30-50 microns.
3. The system as recited in claim 1, further comprising: and the tail gas purifying unit is connected with the tail gas outlet.
4. A method of pretreating chlorosilane residual using the system of any one of claims 1 to 3, comprising:
(1) Supplying nitrogen to the chlorosilane residual liquid equipment through the first gas transmission pipeline by adopting the nitrogen storage tank so as to perform solid-liquid separation on the chlorosilane residual liquid to obtain liquid materials and solid particles respectively, stopping discharging the liquid materials, and volatilizing the chlorosilane residual on the surface of the solid particles along with the nitrogen into tail gas to obtain chlorosilane residues;
(2) And after the tail gas is exhausted and no obvious acid mist exists, closing the first valve, and adopting the liquid ammonia supply unit to supply ammonia gas to the chlorosilane residual liquid equipment through the second gas pipeline so as to enable the chlorosilane residues to react with the ammonia gas, thereby obtaining a solid reactant containing silicon imine, ammonium chloride and metal complex.
5. The method according to claim 4, wherein the ammonia gas pressure after passing through the pressure reducing valve of the liquid ammonia supply unit is 2 to 3bar.
6. The method as recited in claim 4, further comprising:
(3) The temperature of the chlorosilane residual liquid equipment is higher than 300 ℃, and nitrogen is supplied to the feeding area through the third gas transmission pipeline by utilizing the nitrogen storage tank.
7. The method of claim 6, wherein step (3) further comprises controlling the opening of the second valve and the third valve with the control unit based on a display of a temperature detection device on the chlorosilane raffinate plant.
8. The method according to claim 4, characterized in that the exhaust gas is supplied to the exhaust gas purification unit for purification treatment.
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| CN113372373B (en) * | 2021-06-09 | 2022-05-17 | 江西蓝星星火有机硅有限公司 | Device and method for purifying hydrolysate of dimethyl hydrochlorosilane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732746A (en) * | 1986-04-18 | 1988-03-22 | Ford Motor Company | Method of making high purity silicon nitride precursor |
| CN103354802A (en) * | 2011-02-14 | 2013-10-16 | 赢创德固赛有限公司 | Monochlorosilane, process and apparatus for producing same |
| CN204735022U (en) * | 2015-06-02 | 2015-11-04 | 中国恩菲工程技术有限公司 | Purification recovery unit of chlorosilane waste liquid |
| CN206188406U (en) * | 2016-11-18 | 2017-05-24 | 江苏中能硅业科技发展有限公司 | A device for handling polycrystalline silicon by -product sediment thick liquid |
| CN109231217A (en) * | 2018-10-17 | 2019-01-18 | 中国恩菲工程技术有限公司 | The system and method that chlorosilane raffinate chilling removes metal chloride |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN211920882U (en) * | 2020-01-19 | 2020-11-13 | 中国恩菲工程技术有限公司 | Pretreatment system for chlorosilane residual liquid |
-
2020
- 2020-01-19 CN CN202010060402.6A patent/CN111072033B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732746A (en) * | 1986-04-18 | 1988-03-22 | Ford Motor Company | Method of making high purity silicon nitride precursor |
| CN103354802A (en) * | 2011-02-14 | 2013-10-16 | 赢创德固赛有限公司 | Monochlorosilane, process and apparatus for producing same |
| CN204735022U (en) * | 2015-06-02 | 2015-11-04 | 中国恩菲工程技术有限公司 | Purification recovery unit of chlorosilane waste liquid |
| CN206188406U (en) * | 2016-11-18 | 2017-05-24 | 江苏中能硅业科技发展有限公司 | A device for handling polycrystalline silicon by -product sediment thick liquid |
| CN109231217A (en) * | 2018-10-17 | 2019-01-18 | 中国恩菲工程技术有限公司 | The system and method that chlorosilane raffinate chilling removes metal chloride |
Non-Patent Citations (2)
| Title |
|---|
| 刘蕊 ; 杨素芬 ; 谷利敏 ; 时智宝 ; 汪敬恒 ; .三氯氢硅副产物氯硅烷废液的处理方法研究.河南科学.2020,(03),全文. * |
| 蒯伟 ; 郑斌 ; 宋安宁 ; 侯二林 ; .三氯氢硅提纯系统的废气废液再回收.精细与专用化学品.2012,(08),全文. * |
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