CN104163534A - Method and system of processing chlorosilane waste liquid - Google Patents
Method and system of processing chlorosilane waste liquid Download PDFInfo
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- CN104163534A CN104163534A CN201410369315.3A CN201410369315A CN104163534A CN 104163534 A CN104163534 A CN 104163534A CN 201410369315 A CN201410369315 A CN 201410369315A CN 104163534 A CN104163534 A CN 104163534A
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Abstract
The invention discloses a method and a system of processing a chlorosilane waste liquid. The chlorosilane waste liquid comprises at least one of trichlorosilane, tetrachlorosilane, a silicon powder, polymers and metal chlorides. The method comprises: (1) performing evaporation processing on the chlorosilane waste liquid, so as to obtain gaseous-state light compositions and a post-evaporation solution, wherein the gaseous-state light compositions comprise trichlorosilane and tetrachlorosilane, and the post-evaporation solution comprises the silicon powder, the polymers and the metal chlorides; (2) performing condensation processing on the gaseous-state light compositions, so as to obtain liquid-state light compositions; (3) performing rectification processing on the liquid-state light compositions, so as to obtain a tower-top gas and tower bottoms, wherein the tower-top gas comprises trichlorosilane, and the tower bottoms comprise tetrachlorosilane; (4) employing the silicon powder and hydrogen to perform cold hydrogenation processing on the tower bottoms, so as to obtain trichlorosilane; and (5) employing limewater to perform neutralization processing on the post-evaporation solution, so as to obtain a residue solution. The method is capable of realizing continuous processing on the chlorosilane waste liquid and effectively avoiding obstruction of pipelines.
Description
Technical field
The invention belongs to technical field of polysilicon production, particularly, the present invention relates to a kind of method and system of processing chlorosilane waste liquid.
Background technology
In production of polysilicon, rectifying needs continuous blow-down waste liquid, cold hydrogenation quencher bottom to need intermittently discharged waste liquid at the bottom of weighing tower tower, the main component of waste liquid is: trichlorosilane, silicon tetrachloride, also have a small amount of silica flour, metal chloride, polymkeric substance, wherein, metal chloride is aluminum chloride and/or calcium chloride, polymkeric substance is the polymkeric substance of phosphorus trichloride and/or the polymkeric substance of boron trichloride, these chlorosilane waste liquids are to have the poisonous and harmful liquid of severe corrosive and very easily block system pipeline, equipment, very large to safety and environmental hazard.
Tradition rectifying except heavy tower tower at the bottom of the chlorosilane waste liquid of discharge and the waste liquid of cold hydrogenation intermittently discharged directly go three wastes elution device to process, cause that elution device treatment capacity increases, eluting column stop up serious, drip washing alkali charge increases, the press filtration quantity of slag is large, waste water circulation treatment capacity increase etc., causes enormous pressure to three waste-removing device productions, safety, environmental protection.
Application number is 201210412287.X, name is called and in the patent of invention of " method and apparatus that a kind of interval type reclaims chlorosilane waste liquid in production of polysilicon ", discloses a kind of interval type and recycle in production of polysilicon the method for chlorosilane in washing tower discharge waste liquid, the steps include: it is that the chlorosilane waste liquid intermittent type producing is divided and enters evaporation unit from production of polysilicon, by controlling evaporator temperature 120-180 DEG C, when pressure 0.1-0.6MPa, by trichlorosilane lower boiling point, silicon tetrachloride flashes to gaseous state, then send into recycling after rectifying tower purifying treatment.But the shortcoming that this scheme exists: (1) is because containing a large amount of metal chlorides in waste liquid, wherein obvious with aluminum chloride, the evaporation unit of this liquid waste disposal adopts intermittent type charging, can stop up feeding line, affect evaporation unit and dispose waste liquid, strengthen labor cleaning's amount simultaneously; (2) this liquid waste disposal evaporation unit batch type, evaporation unit top does not have material pipeline to clean in time, can cause evaporation unit device interior and agitator to stop up frequent, cause evaporation unit not dispose waste liquid in time, increase this evaporation unit overhaul of the equipments work, increase drip washing treatment capacity, affect polysilicon system and produce.
Application number is 201110221007.2, name is called the method that discloses negative pressure in the patent of invention of the method for waste chlorsilane in polysilicon produced through modified Simens Method " negative pressure reclaim " and reclaim waste chlorsilane in polysilicon produced through modified Simens Method, the steps include: to collect discarded chlorosilane and be transported to waste tank, waste tank pressure-controlling is at gauge pressure 20-900KPa; Chlorosilane waste liquid dependence in waste tank self pressure reduction enters the vacuum evaporator below absolute pressure 20KPa, and the direct gasification under negative pressure of the chlorosilane in vacuum evaporator becomes chlorosilane gas; By vacuum fan, the chlorosilane gas suction chlorosilane in vacuum evaporator is reclaimed to storage tank, liquefaction forms chlorosilane liquid produced; Residual slag in vacuum evaporator is hydrolyzed, then harmless treatment.But the shortcoming that this scheme exists: it is incomplete that (1) adopts negative pressure to reclaim chlorosilane, does not reclaim chlorosilane solutions of anhydrating completely, causes material to be wasted; (2) residual in vacuum evaporator contains a large amount of high boiling material and can stop up at inwall, and labor cleaning's difficulty is large; (3) in vacuum evaporator, residual slag viscosity is very big, going in hydrolytic process, can cause pipeline often to stop up, and impact is produced.
Therefore, make continuous recovery safety and the stable treatment process of chlorosilane waste liquid become one of bottleneck of being badly in need of in whole polysilicon industry solution.
Summary of the invention
The present invention is intended to solve at least to a certain extent one of technical problem in correlation technique.For this reason, one object of the present invention is to propose a kind of method and system of processing chlorosilane waste liquid, and the method can realize the continuous processing to chlorosilane waste liquid, and can effectively avoid the obstruction of pipeline.
In one aspect of the invention, the present invention proposes a kind of method of processing chlorosilane waste liquid, described chlorosilane waste liquid contain in trichlorosilane, silicon tetrachloride, silica flour, polymkeric substance and metal chloride one of at least, described method comprises:
(1) described chlorosilane waste liquid is carried out to evaporation process, to obtain gaseous light component and the rear liquid of evaporation, wherein, described gaseous light component contains trichlorosilane and silicon tetrachloride, and after described evaporation, liquid contains silica flour, polymkeric substance and metal chloride;
(2) described gaseous light component is carried out to condensation process, to obtain liquid light constituent;
(3) described liquid light constituent is carried out to rectification process, to obtain overhead gas and tower bottoms, wherein, described overhead gas contains trichlorosilane, and described tower bottoms contains silicon tetrachloride;
(4) adopt silica flour and hydrogen to carry out cold hydrogen treatment to described tower bottoms, to obtain trichlorosilane; And
(5) adopt liming to described evaporation after liquid carry out neutralizing treatment, to obtain slag liquid.
Can realize the continuous processing to chlorosilane waste liquid according to the method for the processing chlorosilane waste liquid of the embodiment of the present invention, thereby reduce the quantity discharged of waste liquid, and carry out neutralizing treatment by liquid after the evaporation that evaporation process is obtained, the harmful liquid of severe corrosive can be converted into the slag liquid of environment-friendly type, can effectively avoid the obstruction of pipeline and equipment simultaneously, silicon tetrachloride in the light constituent in addition evaporation process being obtained separates and is converted into by cold hydrogen treatment the trichlorosilane of high added value, thereby can realize the recycle of material, thereby realize the recovery of chlorosilane 90%.
In addition, the method for processing chlorosilane waste liquid according to the above embodiment of the present invention can also have following additional technical characterictic:
In some embodiments of the invention, in step (1), in step (1), described evaporation process is that temperature is to carry out under 85～95 degrees Celsius and the pressure condition that is 0.15～0.25MPa.Thus, can significantly improve vaporization efficiency.
In some embodiments of the invention, described evaporation process is carried out in evaporation withdrawer, and described evaporation withdrawer comprises: body, in described body, limit evaporating space, and be suitable for described chlorosilane waste liquid to carry out evaporation process; Chlorosilane waste liquid entrance, described chlorosilane waste liquid entrance is arranged at the top of described body; Nitrogen inlet, described nitrogen inlet is arranged at the top of described body; Silicon tetrachloride entrance, described silicon tetrachloride entrance is arranged on the top of described body; The outlet of gaseous light component, described gaseous light component outlet is arranged on the top of described body; Steam inlet, described steam inlet is arranged on the sidewall of described body; Vapour outlet, described vapour outlet is arranged at the bottom of described body; And liquid outlet after evaporation, after described evaporation, liquid outlet is arranged at the bottom of described body.Thus, can further improve vaporization efficiency.
In some embodiments of the invention, in described evaporation withdrawer, liquid level is 30～75v%.Thus, can significantly improve the purity of gaseous light component.
In some embodiments of the invention, in step (2), the temperature of described liquid light constituent is 30 degrees Celsius.
In some embodiments of the invention, in step (3), it is to carry out under 0.23～0.28MPa condition with pressure that described rectification process is 55～58 degrees Celsius in tower top temperature.Thus, can significantly improve rectification process efficiency.
In some embodiments of the invention, in step (5), the mass concentration of described liming is 10%.Thus, can significantly improve neutralizing treatment efficiency.
In some embodiments of the invention, before the method for described processing chlorosilane waste liquid is further included in and carries out described neutralizing treatment, in described evaporation withdrawer, pass into nitrogen and silicon tetrachloride in advance, to liquid after described evaporation is discharged to described evaporating space.Thus, can effectively avoid evaporating the obstruction of withdrawer inwall and bottom pipe.
In some embodiments of the invention, described neutralizing treatment carrying out in the time that in described evaporation withdrawer, liquid level is lower than 30v%.
In another aspect of the present invention, the present invention proposes a kind of system of processing chlorosilane waste liquid, this system comprises:
Evaporation unit, described evaporation unit is suitable for described chlorosilane waste liquid to carry out evaporation process, to obtain gaseous light component and the rear liquid of evaporation, wherein, described gaseous light component contains trichlorosilane, silicon tetrachloride and metal chloride, and after described evaporation, liquid contains silica flour, metal chloride and polymkeric substance;
Condensing works, described condensing works is connected with described evaporation unit, and is suitable for described gaseous light component to carry out condensation process, to obtain liquid light constituent;
Rectifier unit, described rectifier unit is connected with described condensing works, and is suitable for described liquid light constituent to carry out rectification process, to obtain overhead gas and tower bottoms, wherein, described overhead gas contains trichlorosilane, described tower bottoms contains silicon tetrachloride;
Cold hydrogenation apparatus, described cold hydrogenation apparatus is connected with described rectifier unit, and is suitable for adopting silica flour and hydrogen to carry out cold hydrogen treatment to described tower bottoms, to obtain trichlorosilane; And
Neutralising arrangement, described neutralising arrangement is connected with described evaporation unit, and after being suitable for adopting liming to described evaporation, liquid carries out neutralizing treatment, to obtain slag liquid.
Can realize the continuous processing to chlorosilane waste liquid according to the system of the processing chlorosilane waste liquid of the embodiment of the present invention, thereby reduce the quantity discharged of waste liquid, and carry out neutralizing treatment by liquid after the evaporation that evaporation process is obtained, the harmful liquid of severe corrosive can be converted into the slag liquid of environment-friendly type, can effectively avoid the obstruction of pipeline and equipment simultaneously, silicon tetrachloride in the light constituent in addition evaporation process being obtained separates and is converted into by cold hydrogen treatment the trichlorosilane of high added value, thereby can realize the recycle of material, thereby realize the recovery of chlorosilane 90%.
In addition, the system of processing chlorosilane waste liquid according to the above embodiment of the present invention can also have following additional technical characterictic:
In some embodiments of the invention, described evaporation unit is evaporation withdrawer, and described evaporation withdrawer comprises: body, in described body, limit evaporating space, and be suitable for described chlorosilane waste liquid to carry out evaporation process; Chlorosilane waste liquid entrance, described chlorosilane waste liquid entrance is arranged at the top of described body; Nitrogen inlet, described nitrogen inlet is arranged at the top of described body; Silicon tetrachloride entrance, described silicon tetrachloride entrance is arranged on the top of described body; The outlet of gaseous light component, described gaseous light component outlet is arranged on the top of described body; Steam inlet, described steam inlet is arranged on the sidewall of described body; Vapour outlet, described vapour outlet is arranged at the bottom of described body; And liquid outlet after evaporation, after described evaporation, liquid outlet is arranged at the bottom of described body.Thus, can significantly improve vaporization efficiency.
In some embodiments of the invention, described evaporation withdrawer further comprises level monitoring device, and described level monitoring device is arranged on the sidewall of described body, and is suitable for monitoring liquid level in described body.Thus, can effectively avoid evaporating the obstruction of withdrawer inwall and bottom pipe.
In some embodiments of the invention, described evaporation withdrawer further comprises device for detecting temperature, and described device for detecting temperature is arranged on the sidewall of described body.
In some embodiments of the invention, the system of described processing chlorosilane waste liquid further comprises control device, described control device is connected with described neutralising arrangement with described level monitoring device respectively, so that the liquid level in described evaporation unit starts described neutralising arrangement during lower than 30v%.
Brief description of the drawings
Fig. 1 is the method flow schematic diagram of processing according to an embodiment of the invention chlorosilane waste liquid;
Fig. 2 is the structural representation of processing according to an embodiment of the invention the evaporation withdrawer adopting in the method for chlorosilane waste liquid;
Fig. 3 is the system architecture schematic diagram of processing according to an embodiment of the invention chlorosilane waste liquid;
Fig. 4 is the system architecture schematic diagram of the processing chlorosilane waste liquid of another embodiment according to the present invention;
Fig. 5 is the system architecture schematic diagram of the processing chlorosilane waste liquid of another embodiment according to the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Be exemplary below by the embodiment being described with reference to the drawings, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, it will be appreciated that, term " " center ", " longitudinally ", " laterally ", " length ", " width ", " thickness ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " vertically ", " level ", " top ", " end " " interior ", " outward ", " clockwise ", " counterclockwise ", " axially ", " radially ", orientation or the position relationship of instructions such as " circumferentially " are based on orientation shown in the drawings or position relationship, only the present invention for convenience of description and simplified characterization, instead of device or the element of instruction or hint indication must have specific orientation, with specific orientation structure and operation, therefore can not be interpreted as limitation of the present invention.
In the present invention, unless otherwise clearly defined and limited, the terms such as term " installation ", " being connected ", " connection ", " fixing " should be interpreted broadly, and for example, can be to be fixedly connected with, and can be also to removably connect, or integral; Can be mechanical connection, can be also electrical connection; Can be to be directly connected, also can indirectly be connected by intermediary, can be the connection of two element internals or the interaction relationship of two elements, unless separately there is clear and definite restriction.For the ordinary skill in the art, can understand as the case may be above-mentioned term concrete meaning in the present invention.
In the present invention, unless otherwise clearly defined and limited, First Characteristic Second Characteristic " on " or D score can be that the first and second features directly contact, or the first and second features are by intermediary indirect contact.And, First Characteristic Second Characteristic " on ", " top " and " above " but First Characteristic directly over Second Characteristic or oblique upper, or only represent that First Characteristic level height is higher than Second Characteristic.First Characteristic Second Characteristic " under ", " below " and " below " can be First Characteristic under Second Characteristic or tiltedly, or only represent that First Characteristic level height is less than Second Characteristic.
In one aspect of the invention, the present invention proposes a kind of method of processing chlorosilane waste liquid.According to embodiments of the invention, chlorosilane waste liquid can contain in trichlorosilane, silicon tetrachloride, silica flour, polymkeric substance and metal chloride one of at least.It should be noted that, if no special instructions, the polymkeric substance that " polymkeric substance " is phosphorus trichloride herein and the polymkeric substance of boron trichloride, " metal chloride " is aluminum chloride and calcium chloride.The method of the processing chlorosilane waste liquid below with reference to Fig. 1-2 to the embodiment of the present invention is described in detail.According to embodiments of the invention, the method comprises:
S100: evaporation process
According to embodiments of the invention, chlorosilane waste liquid is carried out to evaporation process, thereby can obtain light constituent and the rear liquid of evaporation.According to embodiments of the invention, chlorosilane waste liquid can be the continuous blow-down liquid of rectifying at the bottom of except heavy tower tower and the intermittently discharged waste liquid of cold hydrogenation utmost point cooler bottom.According to embodiments of the invention, light constituent can contain trichlorosilane and silicon tetrachloride, and after evaporation, liquid can contain silica flour, metal chloride and polymkeric substance.According to embodiments of the invention, the condition of evaporation process is also not particularly limited, and according to a particular embodiment of the invention, evaporation process can be to carry out under 85～95 degrees Celsius and the pressure condition that is 0.15～0.25MPa in temperature.Contriver finds, can significantly improve chlorosilane waste liquid evaporation efficiency, thereby effectively trichlorosilane is separated from chlorosilane waste liquid with silicon tetrachloride under this condition.
According to embodiments of the invention, evaporation process can be carried out in evaporation withdrawer.Concrete, with reference to figure 2, after evaporation withdrawer 100 comprises body 10, chlorosilane waste liquid entrance 11, nitrogen inlet 12, silicon tetrachloride entrance 13, gaseous light component outlet 14, steam inlet 15, vapour outlet 16 and evaporation, liquid exports 17, according to a particular embodiment of the invention, in body, limit evaporating space, and be suitable for chlorosilane waste liquid to carry out evaporation process; Chlorosilane waste liquid entrance is arranged at the top of body, and is suitable for chlorosilane waste liquid to be supplied in evaporating space; Nitrogen inlet is arranged at the top of body, and is suitable for nitrogen gas supply to evaporating space; Silicon tetrachloride entrance is arranged on the top of body, and is suitable for silicon tetrachloride to be supplied in evaporating space; The outlet of gaseous light component is arranged on the top of body, and is suitable for gaseous light component to discharge evaporating space; After evaporation, liquid outlet is arranged at the bottom of body, and is suitable for liquid after evaporation to discharge evaporating space; Steam inlet is arranged on the sidewall of body, and is suitable for adopting steam to heat evaporating space; Vapour outlet is arranged at the bottom of body, and is suitable for cooling steam to discharge heating jacket.According to embodiments of the invention, evaporation withdrawer may further include level monitoring device 18, device for detecting temperature 19 and magnetic stirring apparatus 20.According to a particular embodiment of the invention, level monitoring device is arranged on the sidewall of body, and is suitable for monitoring liquid level in body; Device for detecting temperature is arranged on the sidewall of body.According to embodiments of the invention, in evaporation withdrawer, liquid level can be 30～75v%.Contriver finds, after liquid level is too low, make liquid level show inaccurate, and easily cause beavy metal impurity to enter follow-up condensation recovery process, thereby making to reclaim beavy metal impurity in chlorosilane exceeds standard, if and the too high solution of liquid level causes the chlorosilane of metal impurities to enter in condensation recovery process with liquid form, cause condensing works to stop up.Thus, set the high 30～75v% of being of liquid level scope and can ensure carrying out smoothly of evaporation process, and in the chlorosilane obtaining, metals content impurity is less.
Concrete, level monitoring device can be liquidometer, when liquid level lower than 30v% or liquid level higher than 75v% alarm, and increase baffle plate exceeding liquidometer 250mm height inwall, thus liquid obstruction after avoiding evaporating; After the evaporation of bottom, liquid exports mounted valve, and before valve, has the lower insert port of liquidometer; Magnetic stirring apparatus is with deceleration device, be used for controlling agitator speed, agitator is with agitating vane, agitating vane and evaporation unit inwall distance are 100～150 millimeters, by stirring, mix with heating, the chlorosilane in chlorosilane waste liquid is separated with gas phase form, then reclaim chlorosilane by condensation; Gaseous light component outlet conduit has distance-transmission pressure gauge, for control pressure at 0.15～0.25MPa; Nitrogen inlet is forced into 0.35MPa for passing into nitrogen to evaporation unit, to being entered to the liming that is 10% with mass concentration in neutralising arrangement, hydraulic pressure after the evaporation that contains silica flour, metal chloride, polymkeric substance and a small amount of silicon tetrachloride carries out neutralization reaction, pass into clean silicon tetrachloride for evaporation unit being stirred to flushing by silicon tetrachloride entrance, thereby after just remaining in the evaporation of evaporation unit inwall and bottom pipe, liquid is flushed in neutralization tank simultaneously.
S200: condensation process
According to embodiments of the invention, gaseous light component obtained above is carried out to condensation process, thereby can obtain liquid light constituent.According to embodiments of the invention, gaseous light component is carried out to condensation process and can adopt recirculated cooling water.According to embodiments of the invention, the temperature of liquid light constituent can be 30 degrees Celsius.Thus, can realize the recycle of material, thereby avoid the waste of material.
S300: rectification process
According to embodiments of the invention, the liquid light constituent obtaining is above carried out to rectification process, thereby can obtain overhead gas and tower bottoms, according to a particular embodiment of the invention, overhead gas can have the trichlorosilane of containing, and tower bottoms can contain silicon tetrachloride.According to embodiments of the invention, it is to carry out under 0.23～0.28MPa condition with pressure that rectification process can be 55～58 degrees Celsius in tower top temperature.Contriver's discovery, the rectification process of carrying out under this condition can significantly improve trichlorosilane and silicon tetrachloride separation efficiency.According to embodiments of the invention, rectification process can adopt high-efficiency guide sieve-plate tower, tower internal diameter is 1100～1300mm, stage number is 70～80, and opening for feed is 32nd～55 blocks of column plates, and tower top working pressure is 0.23～0.28MPaG, service temperature is 55～58 DEG C, tower reactor working pressure is 0.27～0.35MPaG, and service temperature is 77～79 DEG C, and reflux ratio is 43～48.
S400: cold hydrogen treatment
According to embodiments of the invention, adopt silica flour and hydrogen to carry out cold hydrogen treatment to tower bottoms obtained above, thereby can obtain trichlorosilane.According to embodiments of the invention, cold hydrogenation can be to carry out under 510～560 degrees Celsius and the pressure condition that is 3.0～3.5MPa in temperature.In this step, particularly, the chemical equation of generation is: Si+2H
2+ 3SiCl
4→ 4SiHCl
3, thus by cold hydrogen treatment, the trichlorosilane that can be high added value by the converting silicon tetrachloride in chlorosilane waste liquid, and then realize the recycle of material.
S500: neutralizing treatment
According to embodiments of the invention, adopt liming to evaporation obtained above after liquid carry out neutralizing treatment, thereby can obtain slag liquid.According to embodiments of the invention, slag liquid can contain silica flour, Calucium Silicate powder, calcium chloride.According to embodiments of the invention, neutralizing treatment can be carried out in neutralization tank, and the mass concentration of liming can be 10%.According to embodiments of the invention, underway and process before, can be in advance in evaporation withdrawer, pass into nitrogen and silicon tetrachloride, thereby after can evaporation, liquid be discharged evaporating space.Contriver finds, after evaporation, the viscosity of liquid is high, easily cause evaporating withdrawer inwall and bottom pipe is stopped up, therefore regularly evaporation withdrawer is stirred to flushing by accessing silicon tetrachloride from evaporation withdrawer top, thereby liquid after the evaporation of residual evaporation withdrawer inwall and bottom pipe can be flushed in neutralization tank.According to embodiments of the invention, neutralizing treatment can be carrying out during lower than 30v% when liquid level in evaporation withdrawer.In this step, neutralization reaction is as follows:
SiHCl
3+Ca(OH)
2+2H
2O→Si(OH)
4+CaCl
2+H
2；
2SiHCl
3+3H
2O→(HSiO)
2O+6HCl；
SiCl
4+H
2O→H
2SiO
3+4HCl；
H
2SiO
3+Ca(OH)
2→CaSiO
3+2H2O；
2HCl+Ca(OH)
2→CaCl
2+H2O。
Particularly, in the time that evaporation withdrawer liquid level is low to moderate 30%, nitrogen inlet by evaporation withdrawer top is supplied with nitrogen, can silica flour will be contained, after the evaporation of metal chloride and polymkeric substance, hydraulic pressure enters in neutralization tank and carries out neutralization reaction with the liming of 10wt%, by the waste gas obtaining from and tank top discharge and deliver to waste gas eluting column and process, obtained slag liquid is delivered to after agitated pool stirs simultaneously and be supplied to pressure filter and carry out press filtration, in addition, stop up for fear of evaporation withdrawer inwall and bottom pipe, regularly evaporation withdrawer is stirred to flushing from evaporation withdrawer top access silicon tetrachloride, thereby liquid after the evaporation of residual evaporation withdrawer inwall and bottom pipe is flushed in neutralization tank.Thus, by neutralizing treatment, what the harmful liquid in chlorosilane waste liquid with severe corrosive can be converted into environment-friendly type contains silica flour, Calucium Silicate powder and calcium chloride slag liquid.
Can realize the continuous processing to chlorosilane waste liquid according to the method for the processing chlorosilane waste liquid of the embodiment of the present invention, thereby reduce the quantity discharged of waste liquid, and carry out neutralizing treatment by liquid after the evaporation that evaporation process is obtained, the harmful liquid of severe corrosive can be converted into the slag liquid of environment-friendly type, can effectively avoid the obstruction of pipeline and equipment simultaneously, silicon tetrachloride in the light constituent in addition evaporation process being obtained separates and is converted into by cold hydrogen treatment the trichlorosilane of high added value, thereby can realize the recycle of material, thereby realize the recovery of chlorosilane 90%.
In another aspect of the present invention, the present invention proposes a kind of system of processing chlorosilane waste liquid.System below with reference to the processing chlorosilane waste liquid of Fig. 3-4 pair embodiment of the present invention is described in detail.According to embodiments of the invention, this system comprises:
Evaporation unit 100: according to embodiments of the invention, evaporation unit 100 is suitable for chlorosilane waste liquid to carry out evaporation process, thus light constituent and the rear liquid of evaporation can be obtained.According to embodiments of the invention, chlorosilane waste liquid can be the continuous blow-down liquid of rectifying at the bottom of except heavy tower tower and the intermittently discharged waste liquid of cold hydrogenation utmost point cooler bottom.According to embodiments of the invention, light constituent can contain trichlorosilane and silicon tetrachloride, and after evaporation, liquid can contain silica flour, metal chloride and polymkeric substance.According to embodiments of the invention, the condition of evaporation process is also not particularly limited, and according to a particular embodiment of the invention, evaporation process can be to carry out under 85～95 degrees Celsius and the pressure condition that is 0.15～0.25MPa in temperature.Contriver finds, can significantly improve chlorosilane waste liquid evaporation efficiency, thereby effectively trichlorosilane is separated from chlorosilane waste liquid with silicon tetrachloride under this condition.According to embodiments of the invention, evaporation process can be carried out in evaporation withdrawer.Concrete, evaporation withdrawer as shown in Figure 2, after evaporation withdrawer 100 comprises body 10, chlorosilane waste liquid entrance 11, nitrogen inlet 12, silicon tetrachloride entrance 13, gaseous light component outlet 14, steam inlet 15, vapour outlet 16 and evaporation, liquid exports 17, according to a particular embodiment of the invention, in body, limit evaporating space, and be suitable for chlorosilane waste liquid to carry out evaporation process; Chlorosilane waste liquid entrance is arranged at the top of body, and is suitable for chlorosilane waste liquid to be supplied in evaporating space; Nitrogen inlet is arranged at the top of body, and is suitable for nitrogen gas supply to evaporating space; Silicon tetrachloride entrance is arranged on the top of body, and is suitable for silicon tetrachloride to be supplied in evaporating space; The outlet of gaseous light component is arranged on the top of body, and is suitable for gaseous light component to discharge evaporating space; After evaporation, liquid outlet is arranged at the bottom of body, and is suitable for liquid after evaporation to discharge evaporating space; Steam inlet is arranged on the sidewall of body, and is suitable for adopting steam to heat evaporating space; Vapour outlet is arranged at the bottom of body, and is suitable for cooling steam to discharge heating jacket.According to embodiments of the invention, evaporation withdrawer may further include level monitoring device 18, device for detecting temperature 19 and magnetic stirring apparatus 20.According to a particular embodiment of the invention, monitoring device 18 is arranged on the sidewall of body, and is suitable for monitoring liquid level in body; Device for detecting temperature is arranged on the sidewall of body.According to embodiments of the invention, in evaporation withdrawer, liquid level can be 30～75v%.Contriver finds, after liquid level is too low, make liquid level show inaccurate, and easily cause beavy metal impurity to enter follow-up condensation recovery process, thereby making to reclaim beavy metal impurity in chlorosilane exceeds standard, if and the too high solution of liquid level causes the chlorosilane of metal impurities to enter in condensation recovery process with liquid form, cause condensing works to stop up.Thus, set the high 30～75v% of being of liquid level scope and can ensure carrying out smoothly of evaporation process, and in the chlorosilane obtaining, metals content impurity is less.
Condensing works 200: according to embodiments of the invention, condensing works 200 is connected with evaporation unit 100, and be suitable for gaseous light component obtained above to carry out condensation process, thereby liquid light constituent can be obtained.According to embodiments of the invention, gaseous light component is carried out to condensation process and can adopt recirculated cooling water.According to embodiments of the invention, the temperature of liquid light constituent can be 30 degrees Celsius.Thus, can realize the recycle of material, thereby avoid the waste of material.
Rectifier unit 300: according to embodiments of the invention, rectifier unit 300 is connected with condensing works 200, and be suitable for the liquid light constituent obtaining above to carry out rectification process, thereby can obtain overhead gas and tower bottoms, according to a particular embodiment of the invention, overhead gas can have the trichlorosilane of containing, and tower bottoms can contain silicon tetrachloride.According to embodiments of the invention, it is to carry out under 0.23～0.28MPa condition with pressure that rectification process can be 55～58 degrees Celsius in tower top temperature.Contriver's discovery, the rectification process of carrying out under this condition can significantly improve trichlorosilane and silicon tetrachloride separation efficiency.According to embodiments of the invention, rectification process can adopt high-efficiency guide sieve-plate tower, tower internal diameter is 1100～1300mm, stage number is 70～80, and opening for feed is 32nd～55 blocks of column plates, and tower top working pressure is 0.23～0.28MPaG, service temperature is 55～58 DEG C, tower reactor working pressure is 0.27～0.35MPaG, and service temperature is 77～79 DEG C, and reflux ratio is 43～48.
Cold hydrogenation apparatus 400: according to embodiments of the invention, cold hydrogenation apparatus 400 is connected with rectifier unit 300, and be suitable for adopting silica flour and hydrogen to carry out cold hydrogen treatment to tower bottoms obtained above, thus can obtain trichlorosilane.According to embodiments of the invention, cold hydrogenation can be to carry out under 510～560 DEG C and the pressure condition that is 3.0～3.5MPaG in temperature.In this step, particularly, the chemical equation of generation is: Si+2H
2+ 3SiCl
4→ 4SiHCl
3, thus by cold hydrogen treatment, the trichlorosilane that can be high added value by the converting silicon tetrachloride in chlorosilane waste liquid, and then realize the recycle of material.
Neutralising arrangement 500: according to embodiments of the invention, neutralising arrangement 500 is connected with evaporation unit 100, adopt liming to evaporation obtained above after liquid carry out neutralizing treatment, thereby can obtain slag liquid.According to embodiments of the invention, underway and process before, can be in advance in evaporation withdrawer, pass into nitrogen and silicon tetrachloride, thereby after can evaporation, liquid be discharged evaporating space.Contriver finds, after evaporation, the viscosity of liquid is high, easily cause evaporating withdrawer inwall and bottom pipe is stopped up, therefore regularly evaporation withdrawer is stirred to flushing by accessing silicon tetrachloride from evaporation withdrawer top, thereby liquid after the evaporation of residual evaporation withdrawer inwall and bottom pipe can be flushed in neutralization tank.Particularly, nitrogen inlet by evaporation withdrawer top is supplied with nitrogen, can silica flour will be contained, after the evaporation of metal chloride and polymkeric substance, hydraulic pressure enters in neutralization tank and carries out neutralization reaction with the liming of 10wt%, by the waste gas obtaining from and tank top discharge and deliver to waste gas eluting column and process, obtained slag liquid is delivered to after agitated pool stirs simultaneously and be supplied to pressure filter and carry out press filtration, in addition, stop up for fear of evaporation withdrawer inwall and bottom pipe, regularly evaporation withdrawer is stirred to flushing from evaporation withdrawer top access silicon tetrachloride, thereby liquid after the evaporation of residual evaporation withdrawer inwall and bottom pipe is flushed in neutralization tank.Thus, by neutralizing treatment, what the harmful liquid in chlorosilane waste liquid with severe corrosive can be converted into environment-friendly type contains silica flour, Calucium Silicate powder and calcium chloride slag liquid.
Can realize the continuous processing to chlorosilane waste liquid according to the system of the processing chlorosilane waste liquid of the embodiment of the present invention, thereby reduce the quantity discharged of waste liquid, and carry out neutralizing treatment by liquid after the evaporation that evaporation process is obtained, the harmful liquid of severe corrosive can be converted into the slag liquid of environment-friendly type, can effectively avoid the obstruction of pipeline and equipment simultaneously, silicon tetrachloride in the light constituent in addition evaporation process being obtained separates and is converted into by cold hydrogen treatment the trichlorosilane of high added value, thereby can realize the recycle of material, thereby realize the recovery of chlorosilane 90%.
As shown in Figure 4, the system of described processing chlorosilane waste liquid further comprises:
Control device 600: according to embodiments of the invention, control device 600 is connected with neutralising arrangement 500 with liquid level detection device 18, and be suitable for starting neutralising arrangement 500 during lower than 30v% when the liquid level in evaporation unit 100.
Below with reference to specific embodiment, present invention is described, it should be noted that, these embodiment are only descriptive, and do not limit the present invention in any way.
Embodiment
With reference to figure 5, rectifying is supplied in the first storage tank 700 except the intermittently discharged waste liquid of the continuous blow-down liquid at the bottom of heavy tower tower and cold hydrogenation utmost point cooler bottom, then by pump p1, chlorosilane waste liquid is supplied to and in evaporation unit 100, carries out evaporation process, obtain the rear liquid of gaseous light component and evaporation, wherein gaseous light component is discharged to enter from evaporation unit 100 tops and condensing works 200, is carried out condensation process, the liquid light constituent obtaining is delivered in the second storage tank 800, then adopt pump p2 that the liquid light constituent obtaining is delivered to and in rectifier unit 300, carried out rectification process, obtain the overhead gas that contains trichlorosilane and the tower bottoms that contains silicon tetrachloride, the tower bottoms that contains silicon tetrachloride is supplied to cold hydrogenation apparatus 400 and carries out cold hydrogenation with silica flour and hydrogen, thereby the trichlorosilane that is high added value by converting silicon tetrachloride, simultaneously, in the time that evaporation unit liquid level is low to moderate 30%, nitrogen inlet by evaporation unit top is supplied with nitrogen, to contain silica flour, after the evaporation of metal chloride and polymkeric substance, hydraulic pressure enters in neutralising arrangement 500 and carries out neutralization reaction with the liming of 10wt%, waste gas eluting column is discharged and delivered to the waste gas obtaining from neutralising arrangement top to be processed, obtained slag liquid is delivered to after agitated pool stirs simultaneously and be supplied to pressure filter and carry out press filtration, in addition, stop up for fear of evaporation withdrawer inwall and bottom pipe, regularly evaporation withdrawer is stirred to flushing from the silicon tetrachloride entrance access silicon tetrachloride at evaporation withdrawer top, thereby liquid after the evaporation of residual evaporation withdrawer inwall and bottom pipe is flushed in neutralising arrangement.
The polycrystalline silicon production line of 5000t/a, cold hydrogenation unit quencher bottom discharge waste liquid is 0.9t/h, rectification cell heavy constituent discharge waste liquid is 0.55t/h, by the recyclable chlorosilane 1.21t/h of chlorosilane waste liquid recovery system, within 8000 hours, calculate according to annual operation, 1 year recyclable 9680 tons of chlorosilane, saves white lime and consumes 9570 tons, saves and produces water 44695m
3; According to existing market price, 5400 yuan/ton of trichlorosilanes, 600 yuan/ton of white limes, produce 4.5 yuan/m of water
3calculate:
Save trichlorosilane expense=9680 ton × 5400 yuan/ton=52272000 yuan;
Save white lime consumption costs=9570 ton × 600 yuan/ton=5742000 yuan;
Save m3 × 4.5, production water consumption expense=44695 yuan/m3=201127 unit;
Save economic benefit=saving trichlorosilane expense+saving white lime consumption costs+saving production water consumption expense=5821.51 ten thousand yuan.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, to the schematic statement of above-mentioned term not must for be identical embodiment or example.And, specific features, structure, material or the feature of description can one or more embodiment in office or example in suitable mode combination.In addition,, not conflicting in the situation that, those skilled in the art can carry out combination and combination by the feature of the different embodiment that describe in this specification sheets or example and different embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, amendment, replacement and modification.
Claims (14)
1. process a method for chlorosilane waste liquid, described chlorosilane waste liquid contain in trichlorosilane, silicon tetrachloride, silica flour, polymkeric substance and metal chloride one of at least, it is characterized in that, described method comprises:
(1) described chlorosilane waste liquid is carried out to evaporation process, to obtain gaseous light component and the rear liquid of evaporation, wherein, described gaseous light component contains trichlorosilane and silicon tetrachloride, and after described evaporation, liquid contains silica flour, polymkeric substance and metal chloride;
(2) described gaseous light component is carried out to condensation process, to obtain liquid light constituent;
(3) described liquid light constituent is carried out to rectification process, to obtain overhead gas and tower bottoms, wherein, described overhead gas contains trichlorosilane, and described tower bottoms contains silicon tetrachloride;
(4) adopt silica flour and hydrogen to carry out cold hydrogen treatment to described tower bottoms, to obtain trichlorosilane; And
(5) adopt liming to described evaporation after liquid carry out neutralizing treatment, to obtain slag liquid.
2. the method for processing chlorosilane waste liquid according to claim 1, is characterized in that, in step (1), described evaporation process is that temperature is to carry out under 85～95 degrees Celsius and the pressure condition that is 0.15～0.25MPa.
3. the method for processing chlorosilane waste liquid according to claim 1, is characterized in that, described evaporation process is carried out in evaporation withdrawer, and described evaporation withdrawer comprises:
Body, limits evaporating space in described body, is suitable for described chlorosilane waste liquid to carry out evaporation process;
Chlorosilane waste liquid entrance, described chlorosilane waste liquid entrance is arranged at the top of described body;
Nitrogen inlet, described nitrogen inlet is arranged at the top of described body;
Silicon tetrachloride entrance, described silicon tetrachloride entrance is arranged on the top of described body;
The outlet of gaseous light component, described gaseous light component outlet is arranged on the top of described body;
Steam inlet, described steam inlet is arranged on the sidewall of described body;
Vapour outlet, described vapour outlet is arranged at the bottom of described body; And
Liquid outlet after evaporation, after described evaporation, liquid outlet is arranged at the bottom of described body.
4. the method for processing chlorosilane waste liquid according to claim 3, is characterized in that, in described evaporation withdrawer, liquid level is 30～75v%.
5. the method for processing chlorosilane waste liquid according to claim 1, is characterized in that, in step (2), the temperature of described liquid light constituent is 30 degrees Celsius.
6. the method for processing chlorosilane waste liquid according to claim 1, is characterized in that, in step (3), it is to carry out under 0.23～0.28MPa condition with pressure that described rectification process is 55～58 degrees Celsius in tower top temperature.
7. the method for processing chlorosilane waste liquid according to claim 1, is characterized in that, in step (5), the mass concentration of described liming is 10%.
8. the method for processing chlorosilane waste liquid according to claim 3, it is characterized in that, before being further included in and carrying out described neutralizing treatment, in described evaporation withdrawer, pass into nitrogen and silicon tetrachloride in advance, to liquid after described evaporation is discharged to described evaporating space.
9. the method for processing chlorosilane waste liquid according to claim 3, is characterized in that, described neutralizing treatment carrying out in the time that in described evaporation withdrawer, liquid level is lower than 30v%.
10. a system of processing chlorosilane waste liquid, is characterized in that, comprising:
Evaporation unit, described evaporation unit is suitable for described chlorosilane waste liquid to carry out evaporation process, to obtain gaseous light component and the rear liquid of evaporation, wherein, described gaseous light component contains trichlorosilane, silicon tetrachloride and metal chloride, and after described evaporation, liquid contains silica flour, metal chloride and polymkeric substance;
Condensing works, described condensing works is connected with described evaporation unit, and is suitable for described gaseous light component to carry out condensation process, to obtain liquid light constituent;
Rectifier unit, described rectifier unit is connected with described condensing works, and is suitable for described liquid light constituent to carry out rectification process, to obtain overhead gas and tower bottoms, wherein, described overhead gas contains trichlorosilane, described tower bottoms contains silicon tetrachloride;
Cold hydrogenation apparatus, described cold hydrogenation apparatus is connected with described rectifier unit, and is suitable for adopting silica flour and hydrogen to carry out cold hydrogen treatment to described tower bottoms, to obtain trichlorosilane; And
Neutralising arrangement, described neutralising arrangement is connected with described evaporation unit, and after being suitable for adopting liming to described evaporation, liquid carries out neutralizing treatment, to obtain slag liquid.
The system of 11. processing chlorosilane waste liquids according to claim 10, is characterized in that, described evaporation unit is evaporation withdrawer, and described evaporation withdrawer comprises:
Body, limits evaporating space in described body, is suitable for described chlorosilane waste liquid to carry out evaporation process;
Chlorosilane waste liquid entrance, described chlorosilane waste liquid entrance is arranged at the top of described body;
Nitrogen inlet, described nitrogen inlet is arranged at the top of described body;
Silicon tetrachloride entrance, described silicon tetrachloride entrance is arranged on the top of described body;
The outlet of gaseous light component, described gaseous light component outlet is arranged on the top of described body;
Steam inlet, described steam inlet is arranged on the sidewall of described body;
Vapour outlet, described vapour outlet is arranged at the bottom of described body; And
Liquid outlet after evaporation, after described evaporation, liquid outlet is arranged at the bottom of described body.
The system of 12. processing chlorosilane waste liquids according to claim 11, it is characterized in that, described evaporation withdrawer further comprises level monitoring device, and described level monitoring device is arranged on the sidewall of described body, and is suitable for monitoring liquid level in described body.
The system of 13. processing chlorosilane waste liquids according to claim 11, is characterized in that, described evaporation withdrawer further comprises device for detecting temperature, and described device for detecting temperature is arranged on the sidewall of described body.
The system of 14. processing chlorosilane waste liquids according to claim 12, it is characterized in that, further comprise control device, described control device is connected with described neutralising arrangement with described level monitoring device respectively, so that the liquid level in described evaporation unit starts described neutralising arrangement during lower than 30v%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692391A (en) * | 2015-03-03 | 2015-06-10 | 陕西天宏硅材料有限责任公司 | Dry-process recycling method for chloro-silicane-containing slurry in polycrystalline silicon production process |
| CN106621757A (en) * | 2017-02-21 | 2017-05-10 | 德山化工（浙江）有限公司 | Recovery treatment device and treatment method of chlorosilane analysis waste gases |
| CN109607548A (en) * | 2018-12-29 | 2019-04-12 | 内蒙古自治区浩森新材料开发有限公司 | A kind of method and device using polysilicon waste production silicon tetrachloride |
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| CN109607548A (en) * | 2018-12-29 | 2019-04-12 | 内蒙古自治区浩森新材料开发有限公司 | A kind of method and device using polysilicon waste production silicon tetrachloride |
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