CN101817541B - Method and device for separating magnesium chloride hexammoniate during silane production by the magnesium silicide method - Google Patents
Method and device for separating magnesium chloride hexammoniate during silane production by the magnesium silicide method Download PDFInfo
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- CN101817541B CN101817541B CN2010101514983A CN201010151498A CN101817541B CN 101817541 B CN101817541 B CN 101817541B CN 2010101514983 A CN2010101514983 A CN 2010101514983A CN 201010151498 A CN201010151498 A CN 201010151498A CN 101817541 B CN101817541 B CN 101817541B
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Abstract
The invention discloses a method for separating and recycling magnesium chloride hexammoniate and liquid ammonia during silane production by a magnesium silicide method, which comprises the following process steps of: inputting the magnesium chloride hexammoniate and liquid ammonia salt slurry produced during silane production by the magnesium silicide method into a filter; inputting the liquid ammonia coming out of the top of the filter into a liquid ammonia storage tank for recycle; conveying the salt slurry coming out of the lower part of the filter into a dryer through a salt slurry feeder; conveying the ammonia gas coming out of the upper part of the dryer into a condenser to liquefy the ammonia gas in the condenser in which the temperature is lower than 33.5 DEG C below zero; and inputting the ammonia gas into the liquid ammonia storage tank for recycle. The invention further discloses a device implementing the method. With the device and method, the invention realizes large-scale industrial production, and magnesium chloride hexammoniate and liquid ammonia are separated and recycled through a continuous liquid-solid filter with fast separation, high efficiency and little liquid in solid. In addition, the filtered wet magnesium chloride hexammoniate is continuously dried at high temperature with high drying efficiency, and the complex ammonia is effectively recycled.
Description
Technical field
The invention belongs to field of polysilicon technology, relate to a kind of recovery of production of silane accessory substance, relate in particular to a kind of magnesium silicide method and produce the magnesium chloride hexammoniate that produces in the silane process and the separation and recovery method and the device thereof of liquefied ammonia.
Background technology
Silane is widely used in the epitaxial deposition monocrystalline silicon membrane and produces polysilicon film, makes the photosensitive part of non-crystal silicon solar cell and duplicator, replaces traditional toner cartridge with the silicon drum, and in glass industry, is used to produce dark-brown glass.In addition, silane and ethene can generate the silicon carbide super powder under laser active, and silane and ammonia can generate the ultrafine powder of silicon nitride end under laser active.Along with the fast development of photovoltaic industry, domestic silane demand increases rapidly.
Along with the continuous maturation of silane fabricating technology, output constantly increases, and silane prepares the recycling of liquefied ammonia and accessory substance magnesium chloride hexammoniate suspension in the process, is paid attention to by silane research preparation unit gradually.In the existing silane by magnesium silicide method technology of preparing, the recycling of liquefied ammonia and magnesium chloride hexammoniate suspension report is less.One Chinese patent application prospectus CN101659414A (Huawei Pressure Container Manufacturing Co., Ltd., Xian Space. Silicomethane low-temperature production and byproduct comprehensive recycling process. open day 2010-03-03.) reported that serialization reclaims liquefied ammonia in the reaction mass; Simultaneously magnesium chloride hexammoniate is simply dried and reclaim remaining ammonia; Make the recycling of liquefied ammonia realize serialization and obtain recycling; Reduce the consumption of liquefied ammonia, reduced environmental pollution.Not enough below but the recovery of liquefied ammonia exists in this method:
(1) recovery of liquefied ammonia is that method through sedimentation realizes that the sedimentation time is long in liquefied ammonia and the magnesium chloride hexammoniate suspension, and production scale is restricted;
(2) solids content of magnesium chloride hexammoniate liquefied ammonia turbid solution low (being no more than 40%) after the sedimentation needs vaporization to separate a large amount of liquefied ammonia in follow-up drying course, and energy consumption is huge;
(3) magnesium chloride hexammoniate after the sedimentation has only carried out simple oven dry, and the ammonia of complexing fails effectively to recycle in the magnesium chloride hexammoniate, and the ammonia consumption is big, and ammonia wherein can continue performance, gives surrounding environment and health deleterious impact.
(4) can't realize large-scale industrial production.
Summary of the invention
The objective of the invention is to; The recycling of producing the liquefied ammonia that produces in the silane process and magnesium chloride hexammoniate suspension to present magnesium silicide method exists that production scale is little, energy consumption big, ammonia reclaims deficiency insufficient, contaminated environment, provides a kind of magnesium silicide method to produce the separation and recovery method of magnesium chloride hexammoniate and liquefied ammonia in the silane process.
Another purpose of the present invention is, the separating and reclaiming device that provides a kind of magnesium silicide method to produce magnesium chloride hexammoniate and liquefied ammonia in the silane process is to satisfy the arts demand of the inventive method.
Fig. 1 has provided the inventive method flow process and device schematic block diagram.The basic principle of the inventive method is: magnesium chloride hexammoniate liquefied ammonia suspension (being commonly called as salt slurry) is sent into the airtight filtration of filter, and clear liquid is got back to the reaction system recycled.Magnesium chloride hexammoniate drains the liquid slurry in the filter after the cartridge surface deposition reaches certain thickness; In filter, feed gas filter cake is pushed further recovery liquefied ammonia wherein, reduce the water capacity of filter cake, gas can be nitrogen, air or ammonia; The gas that feeds again after the preheating reclaims the vaporization of the liquefied ammonia in the filter cake, and gas can be nitrogen, air or ammonia; At last with the filter cake removal.
The separation and recovery method of magnesium chloride hexammoniate and liquefied ammonia comprises the steps: in the magnesium silicide method production silane process of the present invention
A, magnesium silicide method produced the magnesium chloride hexammoniate liquefied ammonia salt slurry input filter that produces in the silane process;
B, the liquefied ammonia input liquefied ammonia storage tank that comes out from filter top recycle;
C, the salt slurry solid that comes out from the filter bottom are sent into drying machine with the salt slurry feeder;
D, the ammonia that comes out from drying machine top are sent into condenser, ammonia is lower than in temperature in-33.5 ℃ the condenser liquefies;
E, the liquefied ammonia input liquefied ammonia storage tank that liquefaction is obtained recycle.
In the said steps A, can remove the flow of filter, preferably adopt pump with pump or valve control magnesium chloride hexammoniate liquefied ammonia salt slurry.
As a kind of embodiment preferred, before the salt slurry filter salt slurry medial launder is set in the said steps A, salt slurry at first is admitted in the said medial launder and stores, again with being pumped into the salt slurry filter.Adopt this method, can control the flow of salt slurry better, guarantee the stable operation in the industrializing implementation process.
In the above-mentioned filter process, after filter cake reaches certain thickness, drain the liquid slurry in the filter, in filter, feed ammonia filter cake is pushed, further reclaim liquefied ammonia wherein, reduce the water capacity of filter cake; And then the ammonia of feeding preheating, the vaporization of the liquefied ammonia in the filter cake is reclaimed, the liquid holdup in the filter cake further descends.
In the said step e liquefied ammonia liquefied ammonia storage tank of packing into is recycled, can directly liquefied ammonia be sent into the liquefied ammonia storage tank with pump.
As a kind of embodiment preferred, after the condenser liquefied ammonia accumulator tank is set in the said step e, liquefied ammonia at first is admitted in the said accumulator tank and stores, again with being pumped into liquid ammonia storage tank.Adopt this method, can be so that industrialization continous-stable reliability of operation obviously improves.
The separating and reclaiming device of magnesium chloride hexammoniate and liquefied ammonia in a kind of preferred magnesium silicide method production silane process, this device comprises salt slurry extraction pump, salt slurry medial launder, filter, salt slurry feeder, drying machine, condenser, liquefied ammonia storage tank, liquefied ammonia accumulator tank; Wherein, Salt slurry extraction delivery side of pump is connected with salt slurry medial launder top inlet, and the lower part outlet of salt slurry medial launder links to each other with the salt slurry filter pump, and salt slurry filters delivery side of pump and links to each other with filter; The top liquefied ammonia discharge nozzle of filter links to each other with the liquefied ammonia storage tank; The salt slurry solid discharging opening of filter bottom links to each other with the salt slurry feeder, and the outlet of salt slurry feeder links to each other with drying machine, and the top of drying machine has at least an ammonia gas outlet to link to each other with condenser; Condenser links to each other with the liquefied ammonia accumulator tank, and the liquefied ammonia accumulator tank reclaims pump through liquefied ammonia and links to each other with the liquefied ammonia storage tank.
Filter is the main equipment of apparatus of the present invention.
The preferred built-in filer element type close filter of said salt slurry filter guarantees that ammonia is enclosed in the filtration system in the filter process, and is free from environmental pollution, the protection workers'health.
Said filter can adopt normal pressure, negative pressure or positive pressure operation; Preferred positive pressure operation reduces the solid water capacity to improve the rate of filtration, and operating pressure is 0.2～2.0MPa, preferred 1.0MPa.
Said filter element can be filter cloth, metal sintering pipe or ceramic post sintering pipe etc.; Preferred skeleton supports the outer filter cloth that covers, and selecting filter cloth for use mainly is that course of industrialization enforcement is convenient, and cost is starkly lower than metal sintering pipe or ceramic post sintering pipe simultaneously.
As a kind of preferred scheme, filter can adopt plural parallel stage, and to realize continuous operation, progression is at least 2 grades, preferably 3 or 4 grades.
The drying machine that the present invention uses can be helicoid screw dryer or pneumatic drier etc., and preferred helicoid screw dryer can be dried more up hill and dale, because helicoid screw dryer can provide stable heat, dry temperature is selected 400～600 ℃, preferred 450～550 ℃.
Said helicoid screw dryer is external heating jacket or coil pipe, and thermal source can be steam, conduction oil or electrical heating.Built-in spiral can be realized moving of solid material.
Described salt slurry medial launder preferred inner band agitating device and/or external belt EGR to prevent solid sedimentation in the salt slurry, make that solid evenly distributes in the salt slurry, are convenient to continuous operation.
Said salt slurry feeder can be screw feeder, Rotary feeder or disk feeder etc., preferred screw feeder, because magnesium chloride hexammoniate contains wet easily sticking wall or obstruction, and screw feeder can be good at solving sticking wall or blockage problem.
Said condenser can be shell and tube, sheet cold type, shell-and-tube or fin tube type, requires preferred shell and tube or sheet cold type in conjunction with practicality and condensation, and chilling temperature is-33.5～60 ℃, preferred-35～45 ℃.
As a kind of embodiment preferred, the outlet of drying machine links to each other with the magnesium chloride packing machine, realizes the serialization packing of magnesium chloride.
The present invention is through liquefied ammonia and magnesium chloride hexammoniate in the liquid-solid filter Separation and Recovery magnesium chloride hexammoniate liquefied ammonia suspension of serialization, and the speed of separation is fast, and efficient is high, and the solid liquid holdup is few; Wet feed magnesium chloride hexammoniate after the filtration has carried out continuous hyperthermia drying, and the efficient of oven dry is high, and the ammonia to complexing in the magnesium chloride hexammoniate has carried out effective recycling simultaneously.
Description of drawings
Fig. 1 is the inventive method flow process and device schematic block diagram;
Fig. 2 is preferred flow process of the inventive method and device sketch map.
Among Fig. 2: 1-liquefied ammonia storage tank; The 2-silane generator; 3-salt slurry extraction pump; 4-salt slurry medial launder; 5-salt slurry filter pump; 6-salt slurry filter; 7-salt slurry feeder; The 8-helicoid screw dryer; 9-magnesium chloride packing machine; 10-cold liquid ammonia condenser; 11-liquefied ammonia accumulator tank; 12-liquefied ammonia reclaims pump.
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is elaborated.
The separating and reclaiming device of magnesium chloride hexammoniate and liquefied ammonia in the magnesium silicide method production silane process of the present invention; Comprise that salt slurry extraction pump 3, salt slurry medial launder 4, salt slurry filter pump 5, filter 6, salt slurry feeder 7, helicoid screw dryer 8, condenser 10, liquefied ammonia storage tank 1, liquefied ammonia accumulator tank 11, liquefied ammonia reclaim pump 12 and magnesium chloride packing machine 9; The outlet of salt slurry extraction pump 3 is connected with salt slurry medial launder 4 tops, salt slurry medial launder 4 subsidiary agitating devices, and the lower part outlet of salt slurry medial launder 4 links to each other with salt slurry filter pump 5; The outlet of salt slurry filter pump 5 links to each other with salt slurry filter 6; Filter 6 is built-in filer element type close filter, and filter core is that skeleton supports the outer filter cloth that covers, and the top liquefied ammonia discharge nozzle of filter 6 links to each other with vertical liquefied ammonia storage tank 1; The salt slurry solid discharging opening of filter 6 bottoms links to each other with screw feeder 7; The outlet of salt slurry feeder 7 links to each other with helicoid screw dryer 8, and the top of drying machine 8 has at least an ammonia gas outlet to link to each other with condenser 10, and drying machine 8 is external chuck heat-conducting oil heating; The outlet of drying machine 8 links to each other with magnesium chloride packing machine 9; Condenser 10 links to each other with liquefied ammonia accumulator tank 11, and condenser 10 adopts the ethanol chuck cooling that is lower than-40 ℃, and liquefied ammonia accumulator tank 11 reclaims pump 12 through liquefied ammonia and links to each other with liquefied ammonia storage tank 1.
Shown in accompanying drawing 2, magnesium chloride hexammoniate separation method in the magnesium silicide method explained hereafter silane process provided by the invention, it comprises the steps:
Liquefied ammonia in the serialization silane generator 2 and magnesium chloride hexammoniate suspension are imported salt slurry medial launders 4 through salt slurry extraction pump 3, and the salt slurry solid content is 20%;
Suspension in the salt slurry medial launder 4 stirs after filter in 3 grades of salt slurry filters 6 of salt slurry filter pump 5 input parallel connection, and filter pressure is 1.0MPa, after filter cake thickness reaches 10cm, drains the liquid slurry in the filter; In filter 6, feed ammonia filter cake is pushed, further reclaim liquefied ammonia wherein, reduce the water capacity of filter cake; The solid liquid holdup is 20%; Feed and be preheated to 20 ℃ ammonia, the vaporization of the liquefied ammonia in the filter cake is reclaimed, the liquid holdup in the filter cake reduces to 5%;
Liquefied ammonia and magnesium chloride hexammoniate suspension are after salt slurry filter 6 filters, and liquefied ammonia is recycled to liquefied ammonia storage tank 1, filter the back solid and get into salt slurry feeder 7;
Filtering the back solid is added in the helicoid screw dryer 8 in 500 ℃ of following continuous feed oven dry by salt slurry feeder 7; The time of staying is 1h; Ammonia gets in the condenser 10 through the ethanol chuck cooling liquefaction that is lower than-40 ℃, and the magnesium chloride after the oven dry gets in the magnesium chloride packing machine 9 and is cooled to 20 ℃ of packings;
Ammonia in the condenser 10 after the liquefaction gets into liquefied ammonia accumulator tank 11 and reclaims in the pump 12 input liquefied ammonia storage tanks 1 for use through liquefied ammonia.
In the inventive method, warp filters and dries the overall recovery of two steps operation ammonia greater than 98%.
Claims (9)
1. a magnesium silicide method is produced the separation and recovery method of magnesium chloride hexammoniate and liquefied ammonia in the silane process, comprises the steps:
A, magnesium silicide method produced the magnesium chloride hexammoniate liquefied ammonia salt slurry input filter that produces in the silane process;
B, the liquefied ammonia input liquefied ammonia storage tank that comes out from filter top recycle;
C, the salt slurry solid that comes out from the filter bottom are sent into drying machine with the salt slurry feeder;
D, the ammonia that comes out from drying machine top are sent into condenser, ammonia is lower than in temperature in-33.5 ℃ the condenser liquefies;
E, the liquefied ammonia input liquefied ammonia storage tank that liquefaction is obtained recycle;
Wherein, in the said steps A magnesium chloride hexammoniate liquefied ammonia salt slurry earlier through salt slurry medial launder input filter again, the suspension in the salt slurry medial launder stirs after filter in 3 grades of salt slurry filters of salt slurry filter pump input parallel connection; Filter pressure is 1.0MPa, after filter cake thickness reaches 10cm, drains the liquid slurry in the filter, in filter, feeds ammonia filter cake is pushed; Further reclaim liquefied ammonia wherein; Reduce the water capacity of filter cake, the solid liquid holdup is 20%, feeds to be preheated to 20 ℃ ammonia again; The vaporization of liquefied ammonia in the filter cake is reclaimed, and the liquid holdup in the filter cake reduces to 5%.
2. separation and recovery method according to claim 1 is characterized in that, the liquefied ammonia liquefied ammonia accumulator tank of packing into is earlier delivered to the liquefied ammonia storage tank again and recycled in the said step e.
3. a magnesium silicide method is produced the separating and reclaiming device of magnesium chloride hexammoniate and liquefied ammonia in the silane process; It is characterized in that this device comprises salt slurry extraction pump (3), salt slurry medial launder (4), filter (6), salt slurry feeder (7), drying machine (8), condenser (10), liquefied ammonia storage tank (1), liquefied ammonia accumulator tank (11); Wherein, The outlet of salt slurry extraction pump (3) is connected with salt slurry medial launder (4) top inlet, and the lower part outlet of salt slurry medial launder (4) links to each other with salt slurry filter pump (5), and salt slurry filters delivery side of pump and links to each other with filter (6); The top liquefied ammonia discharge nozzle of filter (6) links to each other with liquefied ammonia storage tank (1); The salt slurry solid discharging opening of filter (6) bottom links to each other with salt slurry feeder (7), and the outlet of salt slurry feeder (7) links to each other with drying machine (8), and the top of drying machine (8) has at least an ammonia gas outlet to link to each other with condenser (10); Condenser (10) links to each other with liquefied ammonia accumulator tank (11), and liquefied ammonia accumulator tank (11) reclaims pump (12) through liquefied ammonia and links to each other with liquefied ammonia storage tank (1).
4. separating and reclaiming device according to claim 3 is characterized in that, described filter (6) is 2～4 filter parallel connection configurations.
5. according to claim 3 or 4 described separating and reclaiming devices, it is characterized in that described filter (6) is built-in filer element type close filter, said filter core is that skeleton supports outer filter cloth, metal sintering pipe or the ceramic post sintering pipe of covering.
6. separating and reclaiming device according to claim 5 is characterized in that, described drying machine (8) is a helicoid screw dryer.
7. separating and reclaiming device according to claim 3 is characterized in that, described salt slurry medial launder (4) inner band agitating device and/or external belt EGR.
8. separating and reclaiming device according to claim 3 is characterized in that, described salt slurry feeder (7) is a screw feeder.
9. separating and reclaiming device according to claim 3 is characterized in that, described condenser (10) is shell and tube or sheet cold type.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101514983A CN101817541B (en) | 2010-04-21 | 2010-04-21 | Method and device for separating magnesium chloride hexammoniate during silane production by the magnesium silicide method |
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| CN2010101514983A CN101817541B (en) | 2010-04-21 | 2010-04-21 | Method and device for separating magnesium chloride hexammoniate during silane production by the magnesium silicide method |
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| CN101817541B true CN101817541B (en) | 2012-03-21 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101928012B (en) * | 2010-09-13 | 2012-01-11 | 化学工业第二设计院宁波工程有限公司 | Energy utilization method in low-temperature liquid ammonia recovery process |
| CN101928013B (en) * | 2010-09-13 | 2012-03-14 | 化学工业第二设计院宁波工程有限公司 | Method for recycling ammonia in slurry of silane generator |
| CN102974161A (en) * | 2011-09-05 | 2013-03-20 | 田菱精细化工（昆山）有限公司 | Improved structure of filter |
| CN112028096A (en) * | 2020-10-12 | 2020-12-04 | 山西复晟铝业有限公司 | Connecting system for reducing liquid content of seed crystal filter cake and control method |
| CN113479916B (en) * | 2021-08-02 | 2022-09-16 | 青海盐湖工业股份有限公司 | Method and system for large-scale production of anhydrous magnesium chloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249313A (en) * | 2008-04-01 | 2008-08-27 | 南京特种气体厂有限公司 | Recovery cyclic utilization method and apparatus for recovering discharged alkaline air in process of production of silicone hydride with magnesium silicide method |
| CN101659414A (en) * | 2009-09-17 | 2010-03-03 | 西安航天华威化工生物工程有限公司 | Silicomethane low-temperature production and byproduct comprehensive recycling process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249313A (en) * | 2008-04-01 | 2008-08-27 | 南京特种气体厂有限公司 | Recovery cyclic utilization method and apparatus for recovering discharged alkaline air in process of production of silicone hydride with magnesium silicide method |
| CN101659414A (en) * | 2009-09-17 | 2010-03-03 | 西安航天华威化工生物工程有限公司 | Silicomethane low-temperature production and byproduct comprehensive recycling process |
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